Sample records for iridium hexa-halide dianions

  1. Salen complexes with dianionic counterions

    Energy Technology Data Exchange (ETDEWEB)

    Job, Gabriel E.; Farmer, Jay J.; Cherian, Anna E.


    The present invention describes metal salen complexes having dianionic counterions. Such complexes can be readily precipitated and provide an economical method for the purification and isolation of the complexes, and are useful to prepare novel polymer compositions.

  2. Ultrafast Photoinduced Electron Transfer from Peroxide Dianion. (United States)

    Anderson, Bryce L; Maher, Andrew G; Nava, Matthew; Lopez, Nazario; Cummins, Christopher C; Nocera, Daniel G


    The encapsulation of peroxide dianion by hexacarboxamide cryptand provides a platform for the study of electron transfer of isolated peroxide anion. Photoinitiated electron transfer (ET) between freely diffusing Ru(bpy)3(2+) and the peroxide dianion occurs with a rate constant of 2.0 × 10(10) M(-1) s(-1). A competing electron transfer quenching pathway is observed within an ion pair. Picosecond transient spectroscopy furnishes a rate constant of 1.1 × 10(10) s(-1) for this first-order process. A driving force dependence for the ET rate within the ion pair using a series of Ru(bpy)3(2+) derivatives allows for the electronic coupling and reorganization energies to be assessed. The ET reaction is nonadiabatic and dominated by a large inner-sphere reorganization energy, in accordance with that expected for the change in bond distance accompanying the conversion of peroxide dianion to superoxide anion.

  3. Dissociation of dicarboxylate and disulfonate dianions

    NARCIS (Netherlands)

    Ard, S.; Mirsaleh-Kohan, N.; Steill, J. D.; Oomens, J.; Nielsen, S. B.; Compton, R. N.


    Collision-induced dissociation (CID), along with infrared multiple photon dissociation/detachment (IRMPD) techniques, is utilized to study a series of doubly substituted aromatic dianions containing sulfonate and carboxylate functionalities (1,2- and 1,3-benzenedisulfonate, 1,5-naphthalenedisulfonat

  4. On the stabilization of the carbonate dianion by sulfur dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Grein, F.; Chan, J.K.; Liko, I. [New Brunswick Univ., Fredericton, NB (Canada). Dept. of Chemistry


    Dianions CO{sub 3}{sup 2}, SO{sub 4}{sup 2} and other multiply charged anions (MCA) such as PO{sub 4}{sup 3} are not electronically stable in the gas phase. As such, they decay to a lower charge anion by auto electron detachment. The stabilization of dianions and more highly charged anions by common gases was investigated in this study, with particular reference to the stabilization in the gas phase of the carbonate dianion by sulphur dioxide (SO{sub 2}) molecules. Geometries of clusters were optimized by density functional theory (DFT) methods. This paper presented the geometries of different isomers of (SO{sub 2})n and (SO{sub 2})n, for which n = 1-4. Single-point CCSD and CCSD(T) energies at the DFT-optimized geometries were also obtained for n = 1-3. For n = 1 and 2, the monoanionic clusters were adiabatically more stable than the dianionic ones. They became less stable starting at n = 3. The CCSD adiabatic electron detachment energy of the dianionic cluster changed from -0.39 eV for n = 2 to +0.20 eV for n = 3. The vertical electron detachment energy became positive at n = 2, with a CCSD value of 1.35 eV. Many of the less stable dianionic, and most of the monoionic clusters were characterized by the transfer of an oxygen atom from CO{sub 3} to SO{sub 2}. It was concluded that a minimum of 3 water molecules are needed for the stabilization of the sulfate dianion by stepwise hydration. 5 tabs., 1 fig.

  5. Iridium: failures & successes (United States)

    Christensen, CarissaBryce; Beard, Suzette


    This paper will provide an overview of the Iridium business venture in terms of the challenges faced, the successes achieved, and the causes of the ultimate failure of the venture — bankruptcy and system de-orbit. The paper will address technical, business, and policy issues. The intent of the paper is to provide a balanced and accurate overview of the Iridium experience, to aid future decision-making by policy makers, the business community, and technical experts. Key topics will include the history of the program, the objectives and decision-making of Motorola, the market research and analysis conducted, partnering strategies and their impact, consumer equipment availability, and technical issues — target performance, performance achieved, technical accomplishments, and expected and unexpected technical challenges. The paper will use as sources trade media and business articles on the Iridium program, technical papers and conference presentations, Wall Street analyst's reports, and, where possible, interviews with participants and close observers.

  6. Metastable excited states of OBr2- and OCl2- dianions (United States)

    Noorisafa, Zeinab; Sabzyan, Hassan; Keshavarz, Elham


    Electronic stabilities, structures, properties, and spectroscopic constants of the halogen oxide dianions OBr2- and OCl2- and their singly charged anions which are of astrophysical and laboratory interests have been studied. The X2Σ states of OBr2- and OCl2- are metastable with PECs having smooth wells with minima located at R = 1.859 Å and 1.776 Å, and Coulomb barriers of 40402.54987 cm-1 and 43746.63462 cm-1 heights located at RRCB = 2.100 Å and 1.922 Å, respectively, both without any vibrational states. While, the B2Σ state of OBr2- and the A2Σ state of OCl2- are metastable with PECs having wells deep enough to suite several bound states, with minima located at Re = 1.773 Å and 1.6430 Å, and Coulomb barriers of 191437.45813 cm-1 and 180550.70294 cm-1 heights located at RRCB = 2.658 Å and 2.4480 Å, with De = 1.26470 eV and 1.60837 eV, respectively. The OBr- and OCl- singly charged anions are stable in their ground states. Based on the calculated Frank-Condon factors, it is concluded that metastable excited state OBr2- and OCl2- dianions and ground state OBr- and OCl- singly charged anions can be formed via electron capture processes.

  7. Iridium in sea-water. (United States)

    Fresco, J; Weiss, H V; Phillips, R B; Askeland, R A


    Iridium in sea-water has been measured (after isolation from the saline matrix by reduction with magnesium) by neutron bombardment, radiochemical purification and high-resolution gamma-ray spectroscopy. The concentration obtained in a Pacific coastal water was 1.02 +/- 0.26 x 10(-14) g per g of sea-water. At such extremely low concentrations, seawater is an extremely unlikely source for anomalously high iridium concentrations measured in the Cretaceous-Tertiary boundary layer of deep-sea sediments.

  8. Iridium in sea-water

    Energy Technology Data Exchange (ETDEWEB)

    Fresco, J.; Weiss, H.V.; Phillips, R.B.; Askeland, R.A.


    Iridium in sea-water has been measured (after isolation from the saline matrix by reduction with magnesium) by neutron bombardment, radiochemical purification and high resolution ..gamma..-ray spectroscopy. The concentration obtained in a Pacific coastal water was 1.02 +- 0.26 x 10/sup 14/ g per g of sea-water. At such extremely low concentrations, seawater is an extremely unlikely source for anomalously high iridium concentrations measured in the Cretaceous-Tertiary boundary layer of deep-sea sediments.

  9. Iridium-Catalyzed Allylic Substitution (United States)

    Hartwig, John F.; Pouy, Mark J.

    Iridium-catalyzed asymmetric allylic substitution has become a valuable method to prepare products from the addition of nucleophiles at the more substituted carbon of an allyl unit. The most active and selective catalysts contain a phosphoramidite ligand possessing at least one arylethyl substituent on the nitrogen atom of the ligand. In these systems, the active catalyst is generated by a base-induced cyclometalation at the methyl group of this substituent to generate an iridium metalacycle bound by the COD ligand of the [Ir(COD)Cl]2 precursor and one additional labile dative ligand. Such complexes catalyze the reactions of linear allylic esters with alkylamines, arylamines, phenols, alcohols, imides, carbamates, ammonia, enolates and enolate equivalents, as well as typical stabilized carbon nucleophiles generated from malonates and cyanoesters. Iridium catalysts for enantioselective allylic substitution have also been generated from phosphorus ligands with substituents bound by heteroatoms, and an account of the studies of such systems, along with a description of the development of iridium catalysts is included.

  10. The crystal morphology effect of Iridium tris-acetylacetonate on MOCVD iridium coatings (United States)

    Shi, Jing; Hao, Yupeng; Yu, Xiaodong; Tan, Chengwen


    Iridium tris-acetylacetonate is the most commonly used precursor for the metal organic chemical vapour deposition (MOCVD) of iridium coating. In this paper, the crystal morphology effect of iridium tris-acetylacetonate on iridium coatings prepared by MOCVD was studied. Two kinds of Ir(acac)3 crystalline powder were prepared. A precursor sublimation experiment in a fixed bed reactor and an iridium deposition experiment in a cold-wall atmospheric CVD reactor were designed. It is found that the volatility of the hexagonal columnar crystals is better than that of the tetragonal flake crystals under the experimental conditions. It’s due to the hexagonal columnar crystals exposed more crystal faces than the tetragonal flake crystals, increasing its contact area with the transport gas. An adequate supply of iridium tris-acetylacetonate during the pre-deposition period contributed to obtain an iridium coating with a smooth and uniform continuity surface.

  11. Short-Time Events, Coherence, and Structural Dynamics in Photochemistry of Aqueous Halogenated Transition Metal Dianions

    Directory of Open Access Journals (Sweden)

    Pascher T.


    Full Text Available Ultrafast pump-probe spectroscopy, time-resolved x-ray absorption, and computational photochemistry elucidate the photochemical pathway of hexabromoplatinate dianions that propagates through distortions of nascent penta-bromoplatinate anions caused by Jahn-Teller conical intersections and terminates at aquated product complexes.

  12. TCP Performance Enhancement Over Iridium (United States)

    Torgerson, Leigh; Hutcherson, Joseph; McKelvey, James


    In support of iNET maturation, NASA-JPL has collaborated with NASA-Dryden to develop, test and demonstrate an over-the-horizon vehicle-to-ground networking capability, using Iridium as the vehicle-to-ground communications link for relaying critical vehicle telemetry. To ensure reliability concerns are met, the Space Communications Protocol Standards (SCPS) transport protocol was investigated for its performance characteristics in this environment. In particular, the SCPS-TP software performance was compared to that of the standard Transmission Control Protocol (TCP) over the Internet Protocol (IP). This paper will report on the results of this work.

  13. DC Breakdown Experiments with Iridium Cathode

    CERN Document Server

    Profatilova, Iaroslava; Korsback, Anders; Muranaka, Tomoko; Wuensch, Walter


    Electrical breakdown occurring in rf accelerating structures is one of the major disruptions of the accelerated beam in CLIC. At CERN, as complements to rf facilities, DC-spark systems have been used to study breakdown properties of many candidate materials for making rf components. In this note, measurements of conditioning speed, breakdown field and field enhancement factor of iridium are presented comparing with previously tested materials. The average breakdown field after conditioning reached 238 MV/m, which places iridium next to copper. By comparison with results and properties of other metals, the low breakdown field of iridium could be explained by its face-centred-cubic crystal structure.

  14. Enantioselective, iridium-catalyzed monoallylation of ammonia. (United States)

    Pouy, Mark J; Stanley, Levi M; Hartwig, John F


    Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and dienyl carbonates in moderate to good yields and excellent enantioselectivities. This process is enabled by the use of an iridium catalyst that does not require a Lewis acid for activation and that is stable toward a large excess of ammonia. This selective formation of primary allylic amines allows for one-pot syntheses of heterodiallylamines and allylic amides that are not otherwise accessible via iridium-catalyzed allylic amination without the use of blocking groups and protective group manipulations.

  15. On the lack of ring-current aromaticity of (heteroatom) [N]radialenes and their dianions

    NARCIS (Netherlands)

    Domene, C.; Fowler, P.W.; Jenneskens, L.W.; Steiner, E.


    Current-density maps, calculated at the ab initio RHF//6-31G**/ CTOCD-DZ level, show no significant π ring current in planar equilateral geometries ofneutral and dianionic [N]radialenes, oxocarbons and thiocarbons CNYNq- (Y=CH2, O, S; N=4, 5, 6; q=0 (1a-12 a), 2 (1b-12b)). Only the N=3 deltate diani

  16. Sputtered gas-phase dianions detected by high-sensitivity mass spectrometry (United States)

    Gnaser, Hubert; Golser, Robin


    The detection of small doubly-charged molecular anions by means of highly sensitive mass spectrometry is discussed. The production of these gas-phase dianions is accomplished by sputtering the specimen with Cs + ions with an energy of a few keV. It is demonstrated that dianions can be detected most easily when the molecular ion has an odd total mass; then, the dianions will show up at half-integral mass numbers in the mass spectrum. In addition, the agreement of the relative abundances of several isotopomers of a dianion with the nominal isotopic pattern corroborates the identification of a dianionic species in the mass spectrum. These features are exemplified by monitoring mixed silicon-oxygen dianions of the general form OO52-[28], Sn2-[29], SiC62-[30], BeCn2-[31], and PtX62- (X = F, Cl, Br) [32]. More recent work of this group investigated the existence of long-lived dianions containing tetrahedrally coordinated oxygen atoms, namely, O(C)42- and O(BN)42-[33], of cyclic carbon cluster dianions [34], of tetraborates [35], of derivatives of the closo-hexaborate dianion BH62-[36], and of aromatic dianions [37]. Apart from identifying (meta)stable dianions, these computations indicated a possible general formation principle: small dianions are expected to be particularly stable if they consist of a central, at least partially positively charged atom and several equivalent negatively charged ligands [2,6,30,38]. Furthermore, it was pointed out [31,39,40] that for multiply charged anions a repulsive Coulomb barrier for electron emission exists which may result in small metastable dianions which can be detected by mass spectrometry. In fact, the existence of such a Coulomb barrier was inferred from various experiments [41-47]. Apart from dianions, Cederbaum and coworkers studied different small MCAs [19,24,25,48-50]. Theoretical work by other groups [51-59] corroborated and diversified these results. Following the experimental detection of Cn2-[12], several different

  17. Electrochemical investigations of antioxidant interactions with radical anion and dianion of 1,3-dinitrobenzene

    Energy Technology Data Exchange (ETDEWEB)

    Arshad, Nasima [Department of Chemistry, Allama Iqbal Open University, Islamabad (Pakistan); Janjua, Naveed Kausar [Department of Chemistry, Quaid-i-Azam University, Islamabad (Pakistan)], E-mail:; Ahmed, Safeer [Department of Chemistry, Quaid-i-Azam University, Islamabad (Pakistan); Khan, Athar Yaseen [Department of Chemistry, Allama Iqbal Open University, Islamabad (Pakistan); Skibsted, Leif H. [Food Chemistry, Department of Food Science, University of Copenhagen (Denmark)


    Interactions of five antioxidants (AO), quercetin (Q), morin (M), rutin (R), ascorbic acid (AA) and {beta}-carotene ({beta}-C) with anion radical and dianion of 1,3-dinitrobenzene (1,3-DNB) in two aprotic solvents - dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) - have been studied by cyclic voltammetry using glassy carbon electrode. Electrochemical parameters - peak potential (E{sub p}), half-wave potential (E{sub 1/2}), and peak current (i{sub p}) - for the reduction of 1,3-DNB before and after the addition of various concentrations of antioxidants, were evaluated. A gradual decrease in the oxidation peak current and finally irreversibility in 1,3-DNB radical anion and dianion systems upon the addition of antioxidant, reveals their interactions. The homogeneous bi-molecular rate constant (k{sub 2}) was determined from electrochemical data. In comparison to all other antioxidants used, enhanced homogeneous second order rate constant for the interaction of morin with 1,3-DNB anion radical and dianion, was observed. This aspect is attributable to protonation initiated by hydrogen bonding and greater acidic nature of morin.

  18. Formation of nanostructured iridium and polycluster diamond films

    Directory of Open Access Journals (Sweden)

    Pashchenko P. V.


    Full Text Available Iridium films and layered structures "iridium — diamond" were formed on Al2O3, MgO and SrTiO3 substrates. Iridium films were obtained by magnetron sputtering, and polycluster diamond films — by microwave discharge method. Structure of iridium and diamond films was studied depending on formation conditions. Application of polycluster diamond films as heatsink for hybrid microcircuit and control grid of electronic devices was considered.

  19. Study of Ion Specific Interactions of Alkali Cations with Dicarboxylate Dianions

    Energy Technology Data Exchange (ETDEWEB)

    Murdachaew, Garold; Valiev, Marat; Kathmann, Shawn M.; Wang, Xue B.


    Alkali metal cations often show pronounced ion specific interactions and selectivity with macromolecules in biological processes, colloids, and interfacial sciences, but a fundamental understanding about the underlying microscopic mechanism is still very limited. Here we report a direct probe of interactions between alkali metal cations (M{sup +}) and dicarboxylate dianions, O{sub 2}C(CH{sub 2})nCO{sub 2} (D{sub n}{sup 2-}) in the gas phase by combined photoelectron spectroscopy (PES) and ab initio electronic structure calculation on nine M{sup +}-D{sub n}{sup 2-} complexes (M = Li, Na, K; n = 2, 4, 6). PES spectra show that the electron binding energy (EBE) decreases from Li{sup +} to Na{sup +} to K{sup +} for complexes of M{sup +}-D{sub 2}{sup 2-}, whereas the order is Li{sup +} dianion. Theoretical modeling suggests that M{sup +} prefers to interact with both ends of the carboxylate -COOO{sup -} groups by bending the flexible aliphatic backbone, and the local binding environments are found to depend upon dicarboxylate size n and the specific cation M{sup +}. The observed variance of EBEs reflects how well a specific dicarboxylate dianion accommodates each M{sup +}. This work demonstrates the delicate interplay among several factors (electrostatic interaction, size matching, and strain energy) that likely play critical roles in determining the structures and energetics of gaseous clusters as well as ion specificity and selectivity in solutions and biological systems.

  20. Interaction of mono- and dianions with cyanase: evidence for apparent half-site binding. (United States)

    Anderson, P M; Johnson, W V; Endrizzi, J A; Little, R M; Korte, J J


    Cyanase is an inducible enzyme in Escherichia coli that catalyzes bicarbonate-dependent hydrolysis of cyanate. The dianions oxalate, oxalacetate, and malonate are slow-binding inhibitors of cyanase, and some monoanions such as azide and chloride also inhibit cyanase activity [Anderson, P. M., & Little, R. M. (1986) Biochemistry 25, 1621-1626]. The purpose of this study was to investigate the interaction of selected dianions and monoanions by kinetic and equilibrium dialysis binding studies in an effort to obtain information about the active site and catalytic mechanism. Measurement of the effectiveness of 30 different dianions as inhibitors of cyanase showed a significant degree of structural and/or isomeric specificity and considerable variation with respect to the slow-binding nature of the inhibition. Oxalate and oxalacetate both show extreme slow-binding inhibition at very low concentrations. Kinetic studies of the rate of inhibition of cyanase by oxalate showed that the reaction is pseudo first order with respect to oxalate concentration and the results are consistent with a pathway in which oxalate forms a complex with the enzyme in a rapid initial reversible step followed by a slow isomerization step leading to a complex with a very low dissociation constant. The rate of inhibition is significantly reduced by the presence of relatively low concentrations of either azide (analogue of cyanate) or bicarbonate. Equilibrium dialysis binding studies showed that the stoichiometry of binding at saturation for oxalate, malonate, chloride, and bicarbonate is about 0.5 mol of ligand bound/mol of subunit for each compound.(ABSTRACT TRUNCATED AT 250 WORDS)

  1. Unexpected rearrangements in the synthesis of an unsymmetrical tridentate dianionic N-heterocyclic carbene

    KAUST Repository

    Despagnet-Ayoub, Emmanuelle


    Starting from the same ethylenediamine species, three valuable carbene precursors were synthesized under differing conditions: a tridentate dianionic N-heterocyclic carbene bearing an aniline, a phenol and a central dihydroimidazolium salt, its benzimidazolium isomer by intramolecular rearrangement and a dicationic benzimidazolium-benzoxazolium salt by changing the Brønsted acid from HCl to HBF4. A DFT study was performed to understand the rearrangement pathway. The structure of a bis[(NCO)carbene] zirconium complex was determined. © 2013 The Royal Society of Chemistry.

  2. Structures and Energetic Properties of Two New Salts Comprising the 5,5'-Azotetrazolate Dianion

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    Raik Deblitz


    Full Text Available Two new potentially energetic salts comprising the 5,5'-azotetrazolate dianion have been prepared and structurally characterized. The new azotetrazolates are tetraphenylphosphonium-5,5'-azotetrazolate (1 and 1H-1,2,4-triazole-1-carboxamidine-5,5'-azotetrazolate (2. The crystal structures of both compounds have been determined by single-crystal X-ray diffraction and their energetic properties have been tested. Due to its high nitrogen-content of 73.14%, compound 2 was found to be significantly impact-sensitive.

  3. Note: electrochemical etching of sharp iridium tips. (United States)

    Lalanne, Jean-Benoît; Paul, William; Oliver, David; Grütter, Peter H


    We describe an etching procedure for the production of sharp iridium tips with apex radii of 15-70 nm, as determined by scanning electron microscopy, field ion microscopy, and field emission measurements. A coarse electrochemical etch followed by zone electropolishing is performed in a relatively harmless calcium chloride solution with high success rate.

  4. Creep strength of iridium at extremely high temperatures; Zeitstandfestigkeit von Iridium bei extrem hohen Temperaturen

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, B. [Fachhochschule Jena (Germany). Fachbereich Werkstofftechnik; Lupton, D. [Heraeus (W.C.) GmbH, Hanau (Germany). Produktbereich Materialtechnik; Braun, F. [Heraeus (W.C.) GmbH, Hanau (Germany). Produktbereich Materialtechnik; Merker, J. [Jena Univ. (Germany). Technisches Inst.; Helmich, R. [Jena Univ. (Germany). Technisches Inst.


    On iridium in the initial state and after carrying out creep tests, apart from metallographic and fractographic work, investigations on the distribution of trace impurities were done by means of secondary ion mass spectroscopy and investigations of the crystal structure were carried out with the aid of Kossel technique, a special field of X-ray bending. Although iridium of high purity was used for the investigations, enrichment of hydrogen, carbon, sodium, potassium, calcium, magnesium, silicon, iron, nickel and chromium was proved by means of secondary ion mass spectroscopy at the grain boundaries, where the average contents in iridium were only about 1 {mu}g/g. In the creep test, creep fracture lines were found in the range of 1800 to 2300 C and about 0.5 to 12 hours on iridium samples with a square cross section of 1 mm. It follows from the results that this noble metal has a considerable resistance to heat at these temperatures, which makes its use up to 2300 C possible. (orig./RHM) [Deutsch] Es erfolgten am Iridium im Ausgangszustand und nach Durchfuehrung der Zeitstandversuche neben metallographischen und fraktographischen Arbeiten Untersuchungen zur Verteilung der Spurenverunreinigungen mittels Sekundaerionen-Massenspektroskopie sowie Untersuchungen der Kristallstruktur mit Hilfe der Kossel-Technik, einem Spezialgebiet der Roentgenbeugung. Obwohl fuer die Untersuchungen hochreines Iridium verwendet wurde, konnten mittels Sekundaerionen-Massenspektroskopie in den Korngrenzen Anreicherungen von Wasserstoff, Kohlenstoff, Natrium, Kalium, Calcium, Magnesium, Silizium, Eisen, Nickel und Chrom nachgewiesen werden, wobei die durchschnittlichen Gehalte in Iridium nur um 1 {mu}g/g lagen. Im Zeitstandversuch wurden an Iridiumproben mit 1 mm Vierkantquerschnitt Zeitbruchlinien im Bereich von 1800 bis 2300 C und etwa 0,5 bis 12 Stunden aufgenommen. Aus den Ergebnissen folgt, dass das Edelmetall bei diesen Temperaturen noch eine beachtliche Warmfestigkeit besitzt, die

  5. Handling System for Iridium-192 Seeds (United States)

    Carpenter, W.; Wodicka, D.


    A complete system is proposed for safe handling of iridium-192 seeds used to internally irradiate malignant growths. A vibratory hopper feeds the seeds onto a transport system for deposit in a magazine or storage area. A circular magazine consisting of segmented plastic tubing with holes in the walls to accommodate the seeds seems feasible. The magazine is indexed to stop and release a seed for calibration and deposition.

  6. Iridium-Catalyzed Hydrogen Transfer Reactions (United States)

    Saidi, Ourida; Williams, Jonathan M. J.

    This chapter describes the application of iridium complexes to catalytic hydrogen transfer reactions. Transfer hydrogenation reactions provide an alternative to direct hydrogenation for the reduction of a range of substrates. A hydrogen donor, typically an alcohol or formic acid, can be used as the source of hydrogen for the reduction of carbonyl compounds, imines, and alkenes. Heteroaromatic compounds and even carbon dioxide have also been reduced by transfer hydrogenation reactions. In the reverse process, the oxidation of alcohols to carbonyl compounds can be achieved by iridium-catalyzed hydrogen transfer reactions, where a ketone or alkene is used as a suitable hydrogen acceptor. The reversible nature of many hydrogen transfer processes has been exploited for the racemization of alcohols, where temporary removal of hydrogen generates an achiral ketone intermediate. In addition, there is a growing body of work where temporary removal of hydrogen provides an opportunity for using alcohols as alkylating agents. In this chemistry, an iridium catalyst "borrows" hydrogen from an alcohol to give an aldehyde or ketone intermediate, which can be transformed into either an imine or alkene under the reaction conditions. Return of the hydrogen from the catalyst provides methodology for the formation of amines or C-C bonds where the only by-product is typically water.

  7. Simultaneous iridium catalysed oxidation and enzymatic reduction employing orthogonal reagents. (United States)

    Mutti, Francesco G; Orthaber, Andreas; Schrittwieser, Joerg H; de Vries, Johannes G; Pietschnig, Rudolf; Kroutil, Wolfgang


    An iridium catalysed oxidation was coupled concurrently to an asymmetric biocatalytic reduction in one-pot; thus it was shown for the first time that iridium- and alcohol dehydrogenase-catalysed redox reactions are compatible. As a model system racemic chlorohydrins were transformed to enantioenriched chlorohydrins via an oxidation-asymmetric reduction sequence.

  8. Simultaneous iridium catalysed oxidation and enzymatic reduction employing orthogonal reagents

    NARCIS (Netherlands)

    Mutti, Francesco G.; Orthaber, Andreas; Schrittwieser, Joerg H.; Vries, Johannes G. de; Pietschnig, Rudolf; Kroutil, Wolfgang


    An iridium catalysed oxidation was coupled concurrently to an asymmetric biocatalytic reduction in one-pot; thus it was shown for the first time that iridium- and alcohol dehydrogenase-catalysed redox reactions are compatible. As a model system racemic chlorohydrins were transformed to enantioenrich

  9. Hexacoordinate Silicon Compounds with a Dianionic Tetradentate (N,N′,N′,N-Chelating Ligand

    Directory of Open Access Journals (Sweden)

    Daniela Gerlach


    Full Text Available In the context of our systematic investigations of penta- and hexacoordinate silicon compounds, which included dianionic tri- (O,N,O′; O,N,N′ and tetradentate (O,N,N,O; O,N,N′,O′ chelators, we have now explored silicon coordination chemistry with a dianionic tetradentate (N,N′,N′,N chelator. The ligand [o-phenylene-bis(pyrrole-2-carbaldimine, H2L] was obtained by condensation of o-phenylenediamine and pyrrole-2-carbaldehyde and subsequently silylated with chlorotrimethylsilane/triethylamine. Transsilylation of this ligand precursor (Me3Si2L with chlorosilanes SiCl4, PhSiCl3, Ph2SiCl2, (Anis2SiCl2 and (4-Me2N-C6H4PhSiCl2 afforded the hexacoordinate Si complexes LSiCl2, LSiPhCl, LSiPh2, LSi(Anis2 and LSiPh(4-Me2N-C6H4, respectively (Anis = anisyl = 4-methoxyphenyl. 29Si NMR spectroscopy and, for LSiPh2, LSi(Anis2 and LSiPh(4-Me2N-C6H4, single-crystal X-ray diffraction confirm hexacoordination of the Si atoms. The molecular structures of LSiCl2 and LSiPhCl were elucidated by computational methods. Despite the two different N donor sites (pyrrole N, X-type donor; imine N, L-type donor, charge delocalization within the ligand backbone results in compounds with four similar Si–N bonds. Charge distribution within the whole molecules was analyzed by calculating the Natural Charges (NCs. Although these five compounds carry electronically different monodentate substituents, their constituents reveal rather narrow ranges of their charges (Si atoms: +2.10–+2.22; monodentate substituents: −0.54–−0.56; L2−: −1.02–−1.11.

  10. Stereoselective Alkylations of Chiral Nitro Imine and Nitro Hydrazone Dianions. Synthesis of Enantiomerically Enriched 3-Substituted 1-Nitrocyclohexenes† (United States)

    Denmark, Scott E.; Ares, Jeffrey J.


    Dianions of chiral nitro imines (generated by a combination of LDA and s-BuLi) underwent diastereoselective alkylation with methyl, butyl, isopropyl, allyl and methallyl iodides. In contrast to the behavior of simple metalloenamines, the most selective auxiliary contained no coordinating groups, but did possess a large steric difference between the two substituents. The yield and selectivity of the alkylations were improved by the addition of HMPA or DMPU. The use of (S)-1-naphthylethylamine as the auxiliary afforded the R absolute configuration of the alkylation products. This stereochemical outcome could be rationalized by simple steric approach controlled alkylation in a conformationally fixed, internally coordinated dianion. A SAMP nitro hydrazone gave poorer yields and selectivities. PMID:18855478

  11. Self-assembled silver polyhedra with embedded acetylide dianion stabilized by perfluorocarboxylate and 4-hydroxyquinoline ligands. (United States)

    Zhao, Xiao-Li; Wang, Quan-Ming; Mak, Thomas C W


    Four new silver(I) double salts (L(2)H)(4)[Ag(10)(C(2))(CF(3)CO(2))(12)(L)(2)].5H(2)O (1), [Ag(8)(C(2))(CF(3)CO(2))(6)(L)(6)] (2), [(Ag(2)C(2))(AgC(2)F(5)CO(2))(6)(L)(3)(H(2)O)].H(2)O (3), and (L.H(3)O)(2)[Ag(11)(C(2))(2)(C(2)F(5)CO(2))(9)(H(2)O)(2)].H(2)O (4) incorporating the hitherto unexplored ligand 4-hydroxyquinoline (L) have been synthesized by the hydrothermal method. Compound 1 features an unprecedented bicapped square-antiprismatic Ag(10) silver cage with an embedded C(2)(2-) moiety, whereas the discrete supermolecule 2 bears a rhombohedral Ag(8) core similar to that previously found in Ag(2)C(2).6AgNO(3). Compound 3 contains a discrete supramolecular complex whose core is a (C(2))(2)@Ag(16) double cage constructed from the edge-sharing of two monocapped square antiprisms, which is completely surrounded by 12 pentafluoropropionate, 6 4-hydroxyquinoline, and 2 aqua ligands. The layer structure in 4 is constructed from a sinuous anionic silver column composed of fused irregular monocapped trigonal antiprisms each encapsulating a C(2)(2-) dianion, with L.H(3)O(+) species serving as hydrogen-bond connectors to adjacent columns.

  12. Using the charge-stabilization technique in the double ionization potential equation-of-motion calculations with dianion references. (United States)

    Kuś, Tomasz; Krylov, Anna I


    The charge-stabilization method is applied to double ionization potential equation-of-motion (EOM-DIP) calculations to stabilize unstable dianion reference functions. The auto-ionizing character of the dianionic reference states spoils the numeric performance of EOM-DIP limiting applications of this method. We demonstrate that reliable excitation energies can be computed by EOM-DIP using a stabilized resonance wave function instead of the lowest energy solution corresponding to the neutral + free electron(s) state of the system. The details of charge-stabilization procedure are discussed and illustrated by examples. The choice of optimal stabilizing Coulomb potential, which is strong enough to stabilize the dianion reference, yet, minimally perturbs the target states of the neutral, is the crux of the approach. Two algorithms of choosing optimal parameters of the stabilization potential are presented. One is based on the orbital energies, and another--on the basis set dependence of the total Hartree-Fock energy of the reference. Our benchmark calculations of the singlet-triplet energy gaps in several diradicals show a remarkable improvement of the EOM-DIP accuracy in problematic cases. Overall, the excitation energies in diradicals computed using the stabilized EOM-DIP are within 0.2 eV from the reference EOM spin-flip values.

  13. Validation of EXAFS Analysis of Iridium Compounds (United States)

    Feiters, M. C.; Longo, A.; Banerjee, D.; van der Ham, C. J. M.; Hetterscheid, D. G. H.


    Results of iridium L3 edge EXAFS measurements of compounds relevant for water oxidation catalysis are compared to those of other structural techniques. The structural results from EXAFS for the Ir compounds investigated here compare well to those of other structural techniques. Multiple scattering contributions are important in the coordinated Cp* and NHC ligands as well as in the IrCl6 unit and the IrO2 rutile structure. NHC is relatively weak compared to Ir, Cl, and even Cp* and O, and often out of phase with the other contributions.

  14. Ab initio phase diagram of iridium (United States)

    Burakovsky, L.; Burakovsky, N.; Cawkwell, M. J.; Preston, D. L.; Errandonea, D.; Simak, S. I.


    The phase diagram of iridium is investigated using the Z methodology. The Z methodology is a technique for phase diagram studies that combines the direct Z method for the computation of melting curves and the inverse Z method for the calculation of solid-solid phase boundaries. In the direct Z method, the solid phases along the melting curve are determined by comparing the solid-liquid equilibrium boundaries of candidate crystal structures. The inverse Z method involves quenching the liquid into the most stable solid phase at various temperatures and pressures to locate a solid-solid boundary. Although excellent agreement with the available experimental data (to ≲65 GPa) is found for the equation of state (EOS) of Ir, it is the third-order Birch-Murnaghan EOS with B0'=5 rather than the more widely accepted B0'=4 that describes our ab initio data to higher pressure (P ) . Our results suggest the existence of a random-stacking hexagonal close-packed structure of iridium at high P . We offer an explanation for the 14-layer hexagonal structure observed in experiments by Cerenius and Dubrovinsky.

  15. Iridium wire grid polarizer fabricated using atomic layer deposition

    Directory of Open Access Journals (Sweden)

    Knez Mato


    Full Text Available Abstract In this work, an effective multistep process toward fabrication of an iridium wire grid polarizer for UV applications involving a frequency doubling process based on ultrafast electron beam lithography and atomic layer deposition is presented. The choice of iridium as grating material is based on its good optical properties and a superior oxidation resistance. Furthermore, atomic layer deposition of iridium allows a precise adjustment of the structural parameters of the grating much better than other deposition techniques like sputtering for example. At the target wavelength of 250 nm, a transmission of about 45% and an extinction ratio of 87 are achieved.

  16. A porphyrin-stabilized iridium oxide water oxidation catalyst

    National Research Council Canada - National Science Library

    Pillai, Smitha; Gust, Devens; Moore, Ana L; Kodis, Gerdenis; Mallouk, Thomas E; Moore, Thomas A; Bergkamp, Jesse; Sherman, Benjamin D


    Colloidal solutions of iridium oxide hydrate (IrO 2 ·nH 2 O) were formed using porphyrin stabilizers bearing malonate-like functional groups at each of the four meso positions of the porphyrin ring...

  17. Origins of Regioselectivity in Iridium Catalyzed Allylic Substitution


    Madrahimov, Sherzod T.; Li, Qian; Sharma, Ankit; Hartwig, John F.


    Detailed studies on the origin of the regioselectivity for formation of branched products over linear products have been conducted with complexes containing the achiral triphenylphosphite ligand. The combination of iridium and P(OPh)3 was the first catalytic system shown to give high regioselectivity for the branched product with iridium and among the most selective for forming branched products among any combination of metal and ligand. We have shown the active catalyst to be generated from ...

  18. Sputtered iridium oxide films (SIROFs) for neural stimulation electrodes


    Cogan, Stuart F.; Ehrlich, Julia; Plante, Timothy D.; Smirnov, Anton; Shire, Douglas B.; Gingerich, Marcus; Rizzo, Joseph F


    Sputtered iridium oxide films (SIROFs) deposited by DC reactive sputtering from an iridium metal target have been characterized in vitro for their potential as neural recording and stimulation electrodes. SIROFs were deposited over gold metallization on flexible multielectrode arrays fabricated on thin (15 µm) polyimide substrates. SIROF thickness and electrode areas of 200–1300 nm and 1960–125600 µm2, respectively, were investigated. The charge-injection capacities of the SIROFs were evaluat...


    There has been an increasing use of both solid metal and microfabricated iridium electrodes as substrates for various types of electroanalysis. However, investigations to determine heterogeneous electron transfer rate constants on iridium, especially at an electron beam evapor...


    There has been an increasing use of both solid metal and microfabricated iridium electrodes as substrates for various types of electroanalysis. However, investigations to determine heterogeneous electron transfer rate constants on iridium, especially at an electron beam evapor...

  1. Iridium complexes demonstrating broadband emission through controlled geometric distortion and applications thereof

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jian; Turner, Eric


    Iridium compounds and their uses are disclosed herein. For example, carbazole containing iridium compounds are disclosed. The compounds are useful in many devices, including, but not limited to, electroluminescent devices.

  2. Photoionization of tris(2-phenylpyridine)iridium (United States)

    Nemirow, C.; Fine, J.; Lu, Z.; Diri, K.; Krylov, A. I.; Wittig, C.


    The photoionization of gas-phase tris(2-phenylpyridine)iridium (Ir(ppy)3) has been examined. One- and two-photon studies yield a conservative estimate for the upper bound to the ionization energy of 6.4 eV. The one-photon experiment used 193 nm radiation. The latter experiments used tunable UV radiation to excite the ligand-centered 1LC state, which is followed by radiationless decay and photoionization. An accompanying paper presents a theoretical study of excited singlets and triplets and low-energy states of ? . The calculated ionization energy is ∼5.9 eV. The experimental and calculated results together indicate an ionization energy of ∼6 eV. An undulation in the ion yield spectrum (∼270 cm-1 spacing) was observed. It is due to structure in the transition that originates from T1, which is populated through radiationless decay of 1LC. At low fluence, ? is produced without fragmentation, despite the fact that a large amount of vibrational energy is present in T1. Specifically, this vibrational energy is the sum of ? and the thermal energy due to the 177 Ir(ppy)3 vibrational degrees of freedom at 500 K, i.e. the temperature at which the experiments were carried out. This vibrational energy is transported efficiently to the cation.

  3. Iridium mediated phenolic O-H activation and cyclometalation of 2-(naphthyl-1'-azo)-4-methylphenol - Formation of organoiridium complexes

    Indian Academy of Sciences (India)

    Rama Acharyya; Shie-Ming Peng; Gene-Hsiang Lee; Samaresh Bhattacharya


    Reaction of 2-(naphthyl-1'-azo)-4-methylphenol with [Ir(PPh3)3Cl] in refluxing ethanol in the presence of a base (NEt3) affords an organoiridium complex of type [Ir(PPh3)2(L)(H)], where L represents the coordinated 2-(naphthyl-1'-azo)-4-methylphenolate ligand. A similar reaction carried out in toluene affords the [Ir(PPh3)2(L)(H)] complex along with a similar complex of type [Ir(PPh3)2(L)Cl]. Structures of both the [Ir(PPh3)2(L)(H)] and [Ir(PPh3)2(L)Cl] complexes have been determined by X-ray crystallography. In both the complexes, 2-(naphthyl-1'-azo)-4-methylphenol is coordinated to iridium, via C-H activation at the 2' position of the naphthyl ring, as a dianionic tridentate C, N, O-donor and the two triphenylphosphines are trans. The organoiridium complexes show intense MLCT transitions in the visible region. Cyclic voltammetry on the [Ir(PPh3)2(L)(H)] and [Ir(PPh3)2(L)Cl] complexes shows a reversible Ir(III)-Ir(IV) oxidation respectively at 0.55 and 0.73 V vs SCE. An irreversible oxidation of the coordinated 2-(naphthyl-1'-azo)-4-methylphenolate ligand is observed above 1.0 V vs SCE and an irreversible reduction of the same is observed near -1.0 V vs SCE.

  4. Iridium-related deep levels in n-type silicon

    CERN Document Server

    Bollmann, J; Weber, J


    Iridium-related deep levels in n-type silicon were studied by deep level transient spectroscopy (DLTS). Two different sets of samples were used which differ in the Ir-doping process. Stable Ir isotopes were introduced in the melt during the floating-zone growth process. Other samples were implanted with radioactive mercury isotopes, which decay via gold and platinum to iridium or osmium. In these samples an identification of Ir-related levels from the known half-life of the isotopes is possible. Two dominant levels at E/sub c/-0.28 eV and E /sub c/-0.57 eV are assigned to isolated substitutional Ir. Two other levels at E/sub c/-0.17 eV and E/sub c/-0.45 eV are identified as iridium-hydrogen complexes containing one or two hydrogen atoms, respectively. (16 refs).

  5. Platinum-Iridium Alloy Films Prepared by MOCVD

    Institute of Scientific and Technical Information of China (English)

    WEI Yan; CHEN Li; CAI Hongzhong; ZHENG Xu; YANG Xiya; HU Changyi


    Platinum-Iridium alloy films were prepared by MOCVD on Mo substrate using metal-acetylacetonate precursors.Effects of deposition conditions on composition,microstructure and mechanical properties were determined.In these experimental conditions,the purities of films are high and more than 99.0%.The films are homogeneous and monophase solid solution of Pt and Ir.Weight percentage of platinum are much higher than iridium in the alloy.Lattice constant of the alloy changes with the platinum composition.Iridium composition showing an up-down-up trend at the precursor temperature of 190~230℃ and the deposition temperature at 400~550℃.The hardness of Pt-Ir alloys prepared by MOCVD is three times more than the alloys prepared by casting.

  6. Fast regeneration of carotenoids from radical cations by isoflavonoid dianions: importance of the carotenoid keto group for electron transfer. (United States)

    Han, Rui-Min; Chen, Chang-Hui; Tian, Yu-Xi; Zhang, Jian-Ping; Skibsted, Leif H


    Electron transfer to radical cations of beta-carotene, zeaxanthin, canthaxanthin, and astaxanthin from each of the three acid/base forms of the diphenolic isoflavonoid daidzein and its C-glycoside puerarin, as studied by laser flash photolysis in homogeneous methanol/chloroform (1/9) solution, was found to depend on carotenoid structures and more significantly on the deprotonation degree of the isoflavonoids. None of the carotenoid radical cations reacted with the neutral forms of the isoflavonoids while the monoanionic and dianionic forms of the isoflavonoids regenerated the oxidized carotenoid. Electron transfer to the beta-carotene radical cation from the puerarin dianion followed second order kinetics with the rate constant at 25 degrees C k(2) = 5.5 x 10(9) M(-1) s(-1), zeaxanthin 8.5 x 10(9) M(-1) s(-1), canthaxanthin 6.5 x 10(10) M(-1) s(-1), and astaxanthin 11.1 x 10(10) M(-1) s(-1) approaching the diffusion limit and establishing a linear free energy relationship between rate constants and driving force. Comparable results found for the daidzein dianion indicate that the steric hindrance from the glucoside is not important suggesting the more reducing but less acidic 4'-OH/4'-O(-) as electron donors. On the basis of the rate constants obtained from kinetic analyses, the keto group of carotenoids is concluded to facilitate electron transfer. The driving force was estimated from oxidation potentials, as determined by cyclic-voltametry for puerarin and daidzein in aqueous solutions at varying pH conditions, which led to the standard reduction potentials E degrees = 1.13 and 1.10 V versus NHE corresponding to the uncharged puerarin and daidzein. For pH > pK(a2), the apparent potentials of both puerarin and daidzein became constants and were E degrees = 0.69 and 0.65 V, respectively. Electron transfer from isoflavonoids to the carotenoid radical cation, as formed during oxidative stress, is faster for astaxanthin than for the other carotenoids, which may relate

  7. Hydrogen-bond landscapes, geometry and energetics of squaric acid and its mono- and dianions: a Cambridge Structural Database, IsoStar and computational study

    NARCIS (Netherlands)

    F.H. Allen; A.J. Cruz-Cabeza; P.A. Wood; D.A. Bardwell


    As part of a programme of work to extend central-group coverage in the Cambridge Crystallographic Data Centre's (CCDC) IsoStar knowledge base of intermolecular interactions, we have studied the hydrogen-bonding abilities of squaric acid (H(2)SQ) and its mono-and dianions (HSQ(-) and SQ(2-)) using th

  8. Hydrogen-bond landscapes, geometry and energetics of squaric acid and its mono- and dianions: a Cambridge Structural Database, IsoStar and computational study

    NARCIS (Netherlands)

    Allen, F.H.; Cruz-Cabeza, A.J.; Wood, P.A.; Bardwell, D.A.


    As part of a programme of work to extend central-group coverage in the Cambridge Crystallographic Data Centre's (CCDC) IsoStar knowledge base of intermolecular interactions, we have studied the hydrogen-bonding abilities of squaric acid (H(2)SQ) and its mono-and dianions (HSQ(-) and SQ(2-)) using

  9. Synthesis of new heteroscorpionate iridium(I) and iridium(III) complexes. (United States)

    Roa, A E; Campos, J; Paneque, M; Salazar, V; Otero, A; Lara-Sánchez, A; Rodríguez, A M; López-Solera, I; Gómez, M V


    The reactivity of different heteroscorpionate ligands based on bis(pyrazol-1-yl)methane, with different iridium-(i) and -(iii) precursors is reported. The reaction of the heteroscorpionate lithium salts "Li(bdmpza)", [bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate], "Li(bdmpzdta)" [bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate] and "Li(S)-mbpam" [(S)-mbpam = (S)-(-)-N-α-methylbenzyl-2,2-bis(3,5-dimethylpyrazol-1-yl)acetamidate] with 1 equivalent of [IrCl3(THF)3] in THF for 18 h affords high yields of neutral and anionic heteroscorpionate chloride iridium complexes [IrCl2(bdmpza)(THF)] (), [Li(THF)4][IrCl3(bdmpzdta)] () and [IrCl2{(S)-mbpam})(THF)] (). Solution of complex in acetonitrile at room temperature leads to complex [IrCl2{(S)-mbpam})(NCCH3)] (). Complexes and were isolated as enantiopure compounds. The reaction of the lithium salt "Li(bdmpza)" with [IrCl(η(4)-CH2[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]CH2)]2 in THF for 18 h gave the Ir(i) complex [Ir(bdmpza)(η(4)-CH2[double bond, length as m-dash]C(Me)C(Me)[double bond, length as m-dash]CH2)] (). The reaction of complex with CO (2 atm) at room temperature leads to a new complex of Ir(iii), [Ir(bdmpza)(k(2)-CH2C(Me)[double bond, length as m-dash]C(Me)CH2)(CO)] (). Treatment of heteroscorpionate ligand precursors "Li(bdmpza)" and "Li(bdmpzdta)" with [IrCp*Cl2]2 in THF yielded the iridium(iii) complexes [Ir2Cp*2Cl2(bdmpzx)] (x = a , x = dta ). These complexes have helical chirality due to the demands of the fixed pyrazole rings. The stereoisomerism and the self-assembly processes of these helicates have been studied in some detail in solution by NMR spectroscopy and in the solid state by X-ray diffraction. Mixtures of M- and P-handed enantiomers were obtained. Complex undergoes a decarboxylation process initiated by the HCl generated in the previous step leading to the known ionic complex [IrClCp*(bdmpm)][IrCl3Cp*] [bdmpm = bis(3,5-dimethylpyrazol-1-yl)methane] (). The

  10. Homogeneous and heterogenized iridium water oxidation catalysts (United States)

    Macchioni, Alceo


    The development of an efficient catalyst for the oxidative splitting of water into molecular oxygen, protons and electrons is of key importance for producing solar fuels through artificial photosynthesis. We are facing the problem by means of a rational approach aimed at understanding how catalytic performance may be optimized by the knowledge of the reaction mechanism of water oxidation and the fate of the catalytic site under the inevitably harsh oxidative conditions. For the purposes of our study we selected iridium water oxidation catalysts, exhibiting remarkable performance (TOF > 5 s-1 and TON > 20000). In particular, we recently focused our attention on [Cp*Ir(N,O)X] (N,O = 2-pyridincarboxylate; X = Cl or NO3) and [IrCl(Hedta)]Na water oxidation catalysts. The former exhibited a remarkable TOF whereas the latter showed a very high TON. Furthermore, [IrCl(Hedta)]Na was heterogenized onto TiO2 taking advantage of the presence of a dandling -COOH functionality. The heterogenized catalyst maintained approximately the same catalytic activity of the homogeneous analogous with the advantage that could be reused many times. Mechanistic studies were performed in order to shed some light on the rate-determining step and the transformation of catalysts when exposed to "oxidative stress". It was found that the last oxidative step, preceding oxygen liberation, is the rate-determining step when a small excess of sacrificial oxidant is used. In addition, several intermediates of the oxidative transformation of the catalyst were intercepted and characterized by NMR, X-Ray diffractometry and ESI-MS.

  11. Origins of Regioselectivity in Iridium Catalyzed Allylic Substitution. (United States)

    Madrahimov, Sherzod T; Li, Qian; Sharma, Ankit; Hartwig, John F


    Detailed studies on the origin of the regioselectivity for formation of branched products over linear products have been conducted with complexes containing the achiral triphenylphosphite ligand. The combination of iridium and P(OPh)3 was the first catalytic system shown to give high regioselectivity for the branched product with iridium and among the most selective for forming branched products among any combination of metal and ligand. We have shown the active catalyst to be generated from [Ir(COD)Cl]2 and P(OPh)3 by cyclometalation of the phenyl group on the ligand and have shown such species to be the resting state of the catalyst. A series of allyliridium complexes ligated by the resulting P,C ligand have been generated and shown to be competent intermediates in the catalytic system. We have assessed the potential impact of charge, metal-iridium bond length, and stability of terminal vs internal alkenes generated by attack at the branched and terminal positions of the allyl ligand, respectively. These factors do not distinguish the regioselectivity for attack on allyliridium complexes from that for attack on allylpalladium complexes. Instead, detailed computational studies suggest that a series of weak, attractive, noncovalent interactions, including interactions of H-bond acceptors with a vinyl C-H bond of the alkene ligand, favor formation of the branched product with the iridium catalyst. This conclusion underscores the importance of considering attractive interactions, as well as repulsive steric interactions, when seeking to rationalize selectivities.

  12. Achieving Zero Stress in Iridium, Chromium, and Nickle Thin Films (United States)

    Broadway, David M.; Weimer, Jeffrey; Gurgew, Danielle; Lis, Tomasz; Ramsey, Brian D.; O'Dell, Stephen L.; Ames, A.; Bruni, R.


    We examine a method for achieving zero intrinsic stress in thin films of iridium, chromium, and nickel deposited by magnetron sputter deposition. The examination of the stress in these materials is motivated by efforts to advance the optical performance of light-weight x-ray space telescopes into the regime of sub-arc second resolution that rely on control of the film stress to values within 10-100 MPa. A characteristic feature of the intrinsic stress behavior in chromium and nickel is their sensitivity to the magnitude and sign of the intrinsic stress with argon gas pressure, including the existence of a critical pressure that results in zero film stress. This critical pressure scales linearly with the film's density. While the effect of stress reversal with argon pressure has been previously reported by Hoffman and others for nickel and chromium, we have discovered a similar behavior for iridium. Additionally, we have identified zero stress in iridium shortly after island coalescence. This feature of film growth is used for achieving a total internal stress of -2.89 MPa for a 15.8 nm thick iridium film. The surface roughness of this low-stress film was examined using scanning probe microscopy (SPM) and x-ray reflectivity (XRR) at CuKa and these results presented and discussed.

  13. Electrodeposited iridium oxide for neural stimulation and recording electrodes. (United States)

    Meyer, R D; Cogan, S F; Nguyen, T H; Rauh, R D


    Iridium oxide films formed by electrodeposition onto noniridium metal substrates are compared with activated iridium oxide films (AIROFs) as a low impedance, high charge capacity coating for neural stimulation and recording electrodes. The electrodeposited iridium oxide films (EIROFs) were deposited on Au, Pt, PtIr, and 316 LVM stainless steel substrates from a solution of IrCl4, oxalic acid, and K2CO3. A deposition protocol involving 50 potential sweeps at 50 mV/s between limits of 0.0 V and 0.55 V (versus Ag AgCl) followed by potential pulsing between the same limits produced adherent films with a charge storage capacity of >25 mC/cm2. Characterization by cyclic voltammetry and impedance spectroscopy revealed no differences in the electrochemical behavior of EIROF on non-Ir substrates and AIROF. The mechanical stability of the oxides was evaluated by ultrasonication in distilled water followed by dehydration and rehydration. Stability under charge injection was evaluated using 200 micros, 5.9 A/cm2 (1.2 mC/cm2) cathodal pulses. Loss of iridium oxide charge capacity was comparable for AIROFs and the EIROFs, ranging from 1% to 8% of the capacity immediately after activation or deposition. The EIROFs were deposited and evaluated on silicon microprobe electrodes and on metallized polyimide electrodes being developed for neural recording and stimulation applications.

  14. The Iridium (tm) system: Personal communications anytime, anyplace (United States)

    Hatlelid, John E.; Casey, Larry

    The Iridium system is designed to provide handheld personal communications between diverse locations around the world at any time and without prior knowledge of the location of the personal units. This paper provides an overview of the system, the services it provides, its operation, and an overview of the commercial practices and relatively high volume satellite production techniques which will make the system cost effective. A constellation of 66 satellites will provide an orbiting, spherical-shell, infrastructure for this global calling capability. The satellites act as tall cellular towers and allow convenient operation for portable handheld telephones. The system will provide a full range of services including voice, paging, data, geolocation, and fax capabilities. Motorola is a world leader in the production of high volume, high quality, reliable telecommunications hardware. One of Iridium's goals is to apply these production techniques to high reliability space hardware. Concurrent engineering, high performance work teams, advanced manufacturing technologies, and improved assembly and test methods are some of the techniques that will keep the Iridium system cost effective. Mobile, global, flexible personal communications are coming that will allow anyone to call or receive a call from/to anyplace at anytime. The Iridium system will provide communications where none exist today. This connectivity will allow increased information transfer, open new markets for various business endeavors, and in general increase productivity and development.

  15. Iridium-based electrocatalytic systems for the determination of insulin. (United States)

    Pikulski, M; Gorski, W


    Two electrochemical catalytic systems for the determination of insulin were developed. The homogeneous system was based on the oxidation of insulin by chloro complexes of iridium(IV). Kinetic studies revealed that the aquation of iridium complexes activated them toward the oxidation of insulin in acidic solutions; e.g., the rate constant was equal to 25, 900, and 8,400 L mol(-1) s(-1) for the oxidation of insulin by the IrCl62-, Ir(H2O)CI5-, and Ir(H2O)2Cl4 complexes, respectively. The inertness of the iridium complexes argued for the outer-sphere mechanism of the homogeneous oxidation reaction. Electroplating of aquated iridium complexes on the glassy carbon electrode resulted in the formation of the iridium oxide (IrOx) surface film, which was used in the heterogeneous detection system for insulin. The catalytic activity of the IrOx film toward insulin oxidation was ascribed to a combination of electron-transfer mediation and oxygen transfer which was related to the acid/base chemistry of the film. The IrOx film electrode was used as an amperometric detector for flow injection analysis of insulin in pH 7.40 phosphate buffer. Linear least-squares calibration curves over the range 0.05-0.50 microM (five points) had slopes of 35.2 +/- 0.4 nA microM(-1) and correlation coefficients of 0.999. The detection limit for insulin was 20 nM using the criterion of a signal of 3 times the peak-to-peak noise. The advantageous properties of the detector based on the IrOx film are its inherent stability at physiological pH, high catalytic activity toward insulin oxidation, and simplicity of preparation.

  16. Simulation of dose distribution for iridium-192 brachytherapy source type-H01 using MCNPX

    Energy Technology Data Exchange (ETDEWEB)

    Purwaningsih, Anik [Center for development of nuclear informatics, National Nuclear Energy Agency, PUSPIPTEK, Serpong, Banten 15310 (Indonesia)


    Dosimetric data for a brachytherapy source should be known before it used for clinical treatment. Iridium-192 source type H01 was manufactured by PRR-BATAN aimed to brachytherapy is not yet known its dosimetric data. Radial dose function and anisotropic dose distribution are some primary keys in brachytherapy source. Dose distribution for Iridium-192 source type H01 was obtained from the dose calculation formalism recommended in the AAPM TG-43U1 report using MCNPX 2.6.0 Monte Carlo simulation code. To know the effect of cavity on Iridium-192 type H01 caused by manufacturing process, also calculated on Iridium-192 type H01 if without cavity. The result of calculation of radial dose function and anisotropic dose distribution for Iridium-192 source type H01 were compared with another model of Iridium-192 source.

  17. Simulation of dose distribution for iridium-192 brachytherapy source type-H01 using MCNPX (United States)

    Purwaningsih, Anik


    Dosimetric data for a brachytherapy source should be known before it used for clinical treatment. Iridium-192 source type H01 was manufactured by PRR-BATAN aimed to brachytherapy is not yet known its dosimetric data. Radial dose function and anisotropic dose distribution are some primary keys in brachytherapy source. Dose distribution for Iridium-192 source type H01 was obtained from the dose calculation formalism recommended in the AAPM TG-43U1 report using MCNPX 2.6.0 Monte Carlo simulation code. To know the effect of cavity on Iridium-192 type H01 caused by manufacturing process, also calculated on Iridium-192 type H01 if without cavity. The result of calculation of radial dose function and anisotropic dose distribution for Iridium-192 source type H01 were compared with another model of Iridium-192 source.

  18. Probing the lowest coordination number of dianionic platinum-cyanide complexes in the gas phase: Dynamics of the charge dissociation process

    DEFF Research Database (Denmark)

    Bojesen, G; Hvelplund, P; Jørgensen, Thomas J. D.


    Low-energy and high-energy collision induced dissociation techniques are used to study the dissociation behavior of the gaseous Pt(CN)(6)(2-) and Pt(CN)(4)(2-) dianion complexes in order to probe the smallest stable dianion complex. Loss of neutral molecules from Pt(CN)(6)(2-) occurs resulting...... in Pt(CN)(5)(2-) and Pt(CN)(4)(2-), but no indication of the existence of Pt(CN)(3)(2-) was found. This indicates that the lifetime of Pt(CN)(3)(2-) is less than 4 mus (the flight time from the collision region to the detector). In contrast, all monoanion platinum-cyanide complexes were observed, i...

  19. Synthesis, Structure and Noncovalent Interactions of Palladium(Ⅱ) Complexes with N-Benzoyl-β-phenylalaninate Dianion and Aromatic Diimine

    Institute of Scientific and Technical Information of China (English)

    CHEN,Yao-Feng(陈耀峰); GONG,Yu-Qiu(龚钰秋); ZHANG,Hua-Song(张华松)


    Two palladiun(Ⅱ) complexes, [Pd(bipy)(BzPhe-N,O) ] and [Pd(phen) (BzPhe-N,O) ] @4H2O were synthesized by reactions between Pd(bipy)Cl2 and BzPheH2 ( N-benzoyl- β-phenylalanine), Pd(phen) Cla and BzPheH2 in water at pH ~ 9, with their structrues determined by X-ray diffraction analysis. The Pd atom is coordinated by two nitrogen atoms of bipy (or phen), the deprotonated amido type nitrogen atom and one of the carboxylic oxygens of BzPhe (BzPhe = N-benzoyl-β-phenylalaninate dianion). In the complex [Pd(phen)(BzPhe-N,O)]@ 4H2O, the side chain of phenvlalanine is located above and approximately parallels to the coordination plane. Both the aromic-aromatic stacking interaction between the phenyl ring of phenylalanine and phen, and the metal ion-aromatic interaction between the phenyi ring of phenylalanine and Pd(Ⅱ) were observed. [Pd(bipy)(BzPhe-N,O) ] has the phenylalanyl side chain oriented outwards from the coordination plane, which is mainly due to the interaction between the carbonyl oxygen atom of the amido group and the phenyl ring of phenylalanine. The reason for the different orientation of phenylalanyl side chain in the complexes was suggested.

  20. Preparation of platinum/iridium scanning probe microscopy tips

    DEFF Research Database (Denmark)

    Sørensen, Alexis Hammer; Hvid, U.; Mortensen, M.W.


    for the production of sharp tips. After being etched the tips are ready for use in scanning tunneling microscopes, or they may be bent to form integrated tip/cantilever systems in ordinary commercial atomic force microscopes, being applicable as tapping mode tips and as electrostatic force microscopy tips. ©1999......We report on the development of an etching setup for use in the preparation of platinum/iridium tips for atomic force microscopy and scanning electrostatic force microscopy as well as scanning tunneling microscopy. The etching process is based on a two step electrochemical procedure. The first step....... This mechanism is based on the formation of oxygen and hydrogen at the platinum/iridium electrode when the potential is above the dissociation potential of water (~ 1.23 V) and storage of these products interstitially in the outer layers of the platinum wire. This leads to "microexplosions" that detach fragments...

  1. Blistering during the atomic layer deposition of iridium

    Energy Technology Data Exchange (ETDEWEB)

    Genevée, Pascal, E-mail:, E-mail:; Ahiavi, Ernest; Janunts, Norik; Pertsch, Thomas; Kley, Ernst-Bernhard; Szeghalmi, Adriana, E-mail:, E-mail: [Institut für Angewandte Physik, Friedrich-Schiller-Universität Jena, Max-Wien-Platz 1, 07743 Jena (Germany); Oliva, Maria [Fraunhofer IOF, Albert-Einstein-Strasse 7, 07743 Jena (Germany)


    The authors report on the formation of blisters during the atomic layer deposition of iridium using iridium acetylacetonate and oxygen precursors. Films deposited on fused silica substrates led to sparsely distributed large blisters while in the case of silicon with native oxide additional small blisters with a high density was observed. It is found that the formation of blisters is favored by a higher deposition temperature and a larger layer thickness. Postdeposition annealing did not have a significant effect on the formation of blisters. Finally, changing purge duration during the film growth allowed us to avoid blistering and evidenced that impurities released from the film in gas phase were responsible for the formation of blisters.

  2. Olefin oxygenation by water on an iridium center. (United States)

    Ghatak, Tapas; Sarkar, Mithun; Dinda, Shrabani; Dutta, Indranil; Rahaman, S M Wahidur; Bera, Jitendra K


    Oxygenation of 1,5-cyclooctadiene (COD) is achieved on an iridium center using water as a reagent. A hydrogen-bonding interaction with an unbound nitrogen atom of the naphthyridine-based ligand architecture promotes nucleophilic attack of water to the metal-bound COD. Irida-oxetane and oxo-irida-allyl compounds are isolated, products which are normally accessed from reactions with H2O2 or O2. DFT studies support a ligand-assisted water activation mechanism.

  3. Prototyping iridium coated mirrors for x-ray astronomy (United States)

    Döhring, Thorsten; Probst, Anne-Catherine; Stollenwerk, Manfred; Emmerich, Florian; Stehlíková, Veronika; Inneman, Adolf


    X-ray astronomy uses space-based telescopes to overcome the disturbing absorption of the Eart&hacute;s atmosphere. The telescope mirrors are operating at grazing incidence angles and are coated with thin metal films of high-Z materials to get sufficient reflectivity for the high-energy radiation to be observed. In addition the optical payload needs to be light-weighted for launcher mass constrains. Within the project JEUMICO, an acronym for "Joint European Mirror Competence", the Aschaffenburg University of Applied Sciences and the Czech Technical University in Prague started a collaboration to develop mirrors for X-ray telescopes. The X-ray telescopes currently developed within this Bavarian- Czech project are of Lobster eye type optical design. Corresponding mirror segments use substrates of flat silicon wafers which are coated with thin iridium films, as this material is promising high reflectivity in the X-ray range of interest. The deposition of the iridium films is based on a magnetron sputtering process. Sputtering with different parameters, especially by variation of the argon gas pressure, leads to iridium films with different properties. In addition to investigations of the uncoated mirror substrates the achieved surface roughness has been studied. Occasional delamination of the iridium films due to high stress levels is prevented by chromium sublayers. Thereby the sputtering parameters are optimized in the context of the expected reflectivity of the coated X-ray mirrors. In near future measurements of the assembled mirror modules optical performances are planned at an X-ray test facility.

  4. Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution (United States)

    Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.


    NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

  5. Rockot Launch Vehicle Commercial Operations for Grace and Iridium Program (United States)

    Viertel, Y.; Kinnersley, M.; Schumacher, I.


    The GRACE mission and the IRIDIUM mission on ROCKOT launch vehicle are presented. Two identical GRACE satellites to measure in tandem the gravitational field of the earth with previously unattainable accuracy - it's called the Gravity Research and Climate Experiment, or and is a joint project of the U.S. space agency, NASA and the German Centre for Aeronautics and Space Flight, DLR. In order to send the GRACE twins into a 500x500 km , 89deg. orbit, the Rockot launch vehicle was selected. A dual launch of two Iridium satellites was scheduled for June 2002 using the ROCKOT launch vehicle from Plesetsk Cosmodrome in Northern Russia. This launch will inject two replacement satellites into a low earth orbit (LEO) to support the maintenance of the Iridium constellation. In September 2001, Eurockot successfully carried out a "Pathfinder Campaign" to simulate the entire Iridium mission cycle at Plesetsk. The campaign comprised the transport of simulators and related equipment to the Russian port-of-entry and launch site and also included the integration and encapsulation of the simulators with the actual Rockot launch vehicle at Eurockot's dedicated launch facilities at Plesetsk Cosmodrome. The pathfinder campaign lasted four weeks and was carried out by a joint team that also included Khrunichev, Russian Space Forces and Eurockot personnel on the contractors' side. The pathfinder mission confirmed the capability of Eurockot Launch Services to perform the Iridium launch on cost and on schedule at Plesetsk following Eurockot's major investment in international standard preparation, integration and launch facilities including customer facilities and a new hotel. In 2003, Eurockot will also launch the Japanese SERVI'S-1 satellite for USEF. The ROCKOT launch vehicle is a 3 stage liquid fuel rocket whose first 2 stages have been adapted from the Russian SS-19. A third stage, called "Breeze", can be repeatedly ignited and is extraordinarily capable of manoeuvre. Rockot can place

  6. Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis (United States)

    Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.


    Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

  7. Iridium-based double perovskites for efficient water oxidation in acid media (United States)

    Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud; Kooyman, Patricia J.; Wezendonk, Tim; Gascon, Jorge; Fu, W. T.; Koper, Marc T. M.


    The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2.

  8. Sputtered iridium oxide films (SIROFs) for low-impedance neural stimulation and recording electrodes. (United States)

    Cogan, S F; Plante, T D; Ehrlich, J


    Iridium oxide films formed by electrochemical activation of iridium metal (AIROF) or by electrochemical deposition (EIROF) are being evaluated as low-impedance charge-injection coatings for neural stimulation and recording. Iridium oxide may also be deposited by reactive sputtering from iridium metal in an oxidizing plasma. The characterization of sputtered iridium oxide films (SIROFs) as coatings for nerve electrodes is reported. SIROFs were characterized by cyclic voltammetry, electrochemical impedance spectroscopy, and potential transient measurements during charge-injection. The surface morphology of the SIROF transitions from smooth to highly nodular with increasing film thickness from 80 nm to 4600 nm. Charge-injection capacities exceed 0.75 mC/cm(2) with 0.75 ms current pulses in thicker films. The SIROF was deposited on both planar and non-planar substrates and photolithographically patterned by lift-off.

  9. Iridium: Global OTH data communications for high altitude scientific ballooning (United States)

    Denney, A.

    beneficial points provided by the Iridium platform include pure global accessibility (as well as polar), cost effectiveness because it is available as a COTS (Commercially Off The Shelf) technology, reliability in that the equipment must operate in extreme conditions (near space), integration and development time into current systems must be minimized. As a bonus Motorola and NAL Research Corporation are developing SBD (Short Burst Data) into the Iridium network. This may lead the way to a global IP (Internet Protocol) node based ballooning platform. The Iridium satellite data modems employ the Iridium Low-Earth Orbit (LEO) satellite network. The scope of this paper is to introduce an OTH communications alternative, albeit not necessarily a primary one, to existing ballooning platforms using COTS based emerging technologies. Design aspects, characteristics, actual flight testing statistics, principles of the Iridium modems and communication paths are described including payload and support instrumentation interfacing. Not limited to high altitude ballooning, the Iridium communications platform opens a new era in remote commanding and data retrieval.

  10. One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling (United States)

    Peshkov, Roman Yu; Chunyan, Wang; Tretyakov, Evgeny V; Shteingarts, Vitalij D


    Summary A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue. The variety of ω-substituted alkyl bromides, including an extra bromine atom, a double bond, cyano and ester groups, as well as a 1,3-dioxane fragment are suitable as alkylation reagents. PMID:27559409

  11. One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

    Directory of Open Access Journals (Sweden)

    Roman Yu. Peshkov


    Full Text Available A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue. The variety of ω-substituted alkyl bromides, including an extra bromine atom, a double bond, cyano and ester groups, as well as a 1,3-dioxane fragment are suitable as alkylation reagents.

  12. Dynamic high-temperature characterization of an iridium alloy in tension

    Energy Technology Data Exchange (ETDEWEB)

    Song, Bo [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Nelson, Kevin [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Jin, Helena [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Lipinski, Ronald J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Bignell, John [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Ulrich, G. B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); George, E. P. [Ruhr Univ., Bochum (Germany)


    Iridium alloys have been utilized as structural materials for certain high-temperature applications, due to their superior strength and ductility at elevated temperatures. The mechanical properties, including failure response at high strain rates and elevated temperatures of the iridium alloys need to be characterized to better understand high-speed impacts at elevated temperatures. A DOP-26 iridium alloy has been dynamically characterized in compression at elevated temperatures with high-temperature Kolsky compression bar techniques. However, the dynamic high-temperature compression tests were not able to provide sufficient dynamic high-temperature failure information of the iridium alloy. In this study, we modified current room-temperature Kolsky tension bar techniques for obtaining dynamic tensile stress-strain curves of the DOP-26 iridium alloy at two different strain rates (~1000 and ~3000 s-1) and temperatures (~750°C and ~1030°C). The effects of strain rate and temperature on the tensile stress-strain response of the iridium alloy were determined. The DOP-26 iridium alloy exhibited high ductility in stress-strain response that strongly depended on both strain rate and temperature.

  13. Iridium catalyzed growth of vertically aligned CNTs by APCVD

    Energy Technology Data Exchange (ETDEWEB)

    Sahoo, R.K.; Jacob, C., E-mail:


    Highlights: • Growth of uniform-diameter vertically-aligned multi-walled CNTs by APCVD. • Use of high melting point low carbon solubility iridium nanoparticles as catalyst. • Optimization of growth time for uniform sized, uniformly aligned CNTs. • Growth model for the various features in the vertically aligned CNTs is proposed. - Abstract: Vertically aligned carbon nanotubes (VA-CNTs) have been synthesized using high temperature catalyst nanoparticles of iridium. The catalyst layer was prepared by DC sputtering. Particle density, circularity and average particle size of the catalyst were analyzed using field emission scanning electron microscopy. The alignment, morphology and the length of the as-grown CNTs were analyzed using field-emission scanning electron microscopy. High resolution transmission electron microscopy was carried out to observe the layers of graphitic stacking which form the carbon nanotubes. Micro Raman measurement was used for the analysis of the graphitic crystallinity of the as-grown carbon nano structures. Effects of growth time variation on growth morphology and alignment have been studied. The alignment has been explained on the basis of the crowding effect of the neighboring nanoparticles.

  14. Asymmetric Hydrogenation of Isoxazolium Triflates with a Chiral Iridium Catalyst. (United States)

    Ikeda, Ryuhei; Kuwano, Ryoichi


    The iridium catalyst [IrCl(cod)]2 -phosphine-I2 (cod=1,5-cyclooctadiene) selectively reduced isoxazolium triflates to isoxazolines or isoxazolidines in the presence of H2 . The iridium-catalyzed hydrogenation proceeded in high-to-good enantioselectivity when an optically active phosphine-oxazoline ligand was used. The 3-substituted 5-arylisoxazolium salts were transformed into 4-isoxazolines with up to 95:5 enantiomeric ratio (e.r.). Chiral cis-isoxazolidines were obtained in up to 89:11 e.r., with no formation of their trans isomers, when the substrates had a primary alkyl substituent at the 5-position. The mechanistic studies indicate that the hydridoiridium(III) species prefers to deliver its hydride to the C5 atom of the isoxazole ring. The hydride attack leads to the formation of the chiral isoxazolidine via a 3-isoxazoline intermediate. Meanwhile, in the selective formation of 4-isoxazolines, hydride attack at the C5 atom may be obstructed by steric hindrance from the 5-aryl substituent. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Analysis and Consequences of the Iridium 33-Cosmos 2251 Collision (United States)

    Anz-Meador, P. D.; Liou, Jer-Chi


    The collision of Iridium 33 and Cosmos 2251, on 10 February 2009, was the first known unintentional hypervelocity collision in space of intact satellites. Iridium 33 was an active commercial telecommunications satellite, while Cosmos 2251 was a derelict communication satellite of the Strela-2M class. The collision occurred at a relative velocity of 11.6 km/s at an altitude of approximately 790 km over the Great Siberian Plain and near the northern apex of Cosmos 2251 s orbit. This paper describes the physical and orbital characteristics of the relevant spacecraft classes and reports upon our analysis of the resulting debris clouds size, mass, area-to-mass ratio, and relative velocity/directionality distributions. We compare these distributions to those predicted by the NASA breakup model and notable recent fragmentation events; in particular, we compare the area-to-mass ratio distribution for each spacecraft to that exhibited by the FY-1C debris cloud for the purpose of assessing the relative contribution of modern aerospace materials to debris clouds resulting from energetic collisions. In addition, we examine the long-term consequences of this event for the low Earth orbit (LEO) environment. Finally, we discuss "lessons learned", which may be incorporated into NASA s environmental models.

  16. Iridium anomaly in the Cretaceous section of the Eastern Kamchatka (United States)

    Savelyev, Dmitry; Savelyeva, Olga


    The origin of iridium anomalies is widely discussed with regard to massive fauna and flora extinction at several geologic boundaries. Two hypotheses are most popular, cosmogenic and volcanogenic. Anomalies of iridium are known at many stratigraphic levels, both at the geologic series borders and within geologic series. Our studies revealed increased content of iridium in a section of Cretaceous oceanic deposits on the Kamchatsky Mys Peninsula (Eastern Kamchatka, Russia). The investigated section (56°03.353´N, 163°00.376´E) includes interbedded jaspers and siliceous limestones overlaying pillow-basalts. These deposits belong to the Smagin Formation of the Albian-Cenomanian age. In the middle and upper parts of the section two beds of black carbonaceous rocks with sapropelic organic matter were observed. Their formation marked likely episodes of oxygen depletion of oceanic intermediate water (oceanic anoxic events). Our geochemical studies revealed an enrichment of the carbonaceous beds in a number of major and trace elements (Al2O3, TiO2, FeO, MgO, K2O, P2O5, Cu, Zn, Ni, Cr, V, Mo, Ba, Y, Zr, Nb, REE, U, Au, Pt etc.) in comparison with associating jaspers and limestones. There are likely different sources which contributed to the enrichment. It is possible however to correlate the excess of Al, Ti, Zr, Nb with volcanogenic admixture, which is absent in limestones and jaspers. A possible source of the volcanogenic material was local volcanism as suggested by the close association of the investigated section with volcanic rocks (basaltic lavas and hyaloclastites). The basalts of the Smagin Formation were previously proposed to originate during Cretaceous activity of the Hawaiian mantle plume (Portnyagin et al., Geology, 2008). Neutron activation analysis indicated increased up to 9 ppb concentration of Ir at the bottom of the lower carbonaceous bed (inorganic part of the sample was analyzed comprising 46% of the bulk rock). In other samples Ir content was below

  17. Hydrogen-bond landscapes, geometry and energetics of squaric acid and its mono- and dianions: a Cambridge Structural Database, IsoStar and computational study. (United States)

    Allen, Frank H; Cruz-Cabeza, Aurora J; Wood, Peter A; Bardwell, David A


    As part of a programme of work to extend central-group coverage in the Cambridge Crystallographic Data Centre's (CCDC) IsoStar knowledge base of intermolecular interactions, we have studied the hydrogen-bonding abilities of squaric acid (H2SQ) and its mono- and dianions (HSQ(-) and SQ(2-)) using the Cambridge Structural Database (CSD) along with dispersion-corrected density functional theory (DFT-D) calculations for a range of hydrogen-bonded dimers. The -OH and -C=O groups of H2SQ, HSQ(-) and SQ(2-) are potent donors and acceptors, as indicated by their hydrogen-bond geometries in available crystal structures in the CSD, and by the attractive energies calculated for their dimers with acetone and methanol, which were used as model acceptors and donors. The two anions have sufficient examples in the CSD for their addition as new central groups in IsoStar. It is also shown that charge- and resonance-assisted hydrogen bonds involving H2SQ and HSQ(-) are similar in strength to those made by carboxylate COO(-) acceptors, while hydrogen bonds made by the dianion SQ(2-) are somewhat stronger. The study reinforces the value of squaric acid and its anions as cocrystal formers and their actual and potential importance as isosteric replacements for carboxylic acid and carboxylate functions.

  18. Theoretical Study on the Stable Structures and Aromaticities for Pnictogen Dianionic Sb2-4, Bi2-4, and (SbBi)2-2 Clusters

    Institute of Scientific and Technical Information of China (English)

    Xing-bao Wang; Xian-xing Chi


    Through the theoretical calculation of structural optimization, vibrational frequencies and atomization energies with one method of density functional theory (B3LYP) and two post-Hartree-Fock approaches (MP2, CCSD(T)), several stable isomers for new three pnictogen dianionic Sb2-4, Bi2-4, and (SbBi)2-2 species were determined. For two homoatomic Sb2-4 and Bi2-4 species, there are three stable isomers: square (D4h), roof-shaped (C2v-1), and C2v-2 structure with the square isomer being the ground state. For the heteroatomic dian-ionic (SbBi)2-2 species, there are also three stable isomers: rhombus (D2h), roof-shaped (C1), and C2v structures with the rhombic isomer being the ground state. The calculated NICS values show that nucleus-independent chemical shifts (NICS) values of roof-shaped isomers for Sb2-4, Bi2-4, and (SbBi)2-2 species are all negative, consequently indicating that these roof-shaped isomers possess aromaticities. NICS values for the planar ring isomers are all positive, suggesting that these three planar ring isomers have antiaromatic characters. The aromaticity for the two stable roof-shaped and square isomers are preliminarily explained and discussed with MO analysis.

  19. Cation-Dependent Stabilization of Electrogenerated Naphthalene Diimide Dianions in Porous Polymer Thin Films and Their Application to Electrical Energy Storage. (United States)

    DeBlase, Catherine R; Hernández-Burgos, Kenneth; Rotter, Julian M; Fortman, David J; Abreu, Dieric dos S; Timm, Ronaldo A; Diógenes, Izaura C N; Kubota, Lauro T; Abruña, Héctor D; Dichtel, William R


    Porous polymer networks (PPNs) are attractive materials for capacitive energy storage because they offer high surface areas for increased double-layer capacitance, open structures for rapid ion transport, and redox-active moieties that enable faradaic (pseudocapacitive) energy storage. Here we demonstrate a new attractive feature of PPNs--the ability of their reduced forms (radical anions and dianions) to interact with small radii cations through synergistic interactions arising from densely packed redox-active groups, only when prepared as thin films. When naphthalene diimides (NDIs) are incorporated into PPN films, the carbonyl groups of adjacent, electrochemically generated, NDI radical anions and dianions bind strongly to K(+), Li(+), and Mg(2+), shifting the formal potentials of NDI's second reduction by 120 and 460 mV for K(+) and Li(+)-based electrolytes, respectively. In the case of Mg(2+), NDI's two redox waves coalesce into a single two-electron process with shifts of 240 and 710 mV, for the first and second reductions, respectively, increasing the energy density by over 20 % without changing the polymer backbone. In contrast, the formal reduction potentials of NDI derivatives in solution are identical for each electrolyte, and this effect has not been reported for NDI previously. This study illustrates the profound influence of the solid-state structure of a polymer on its electrochemical response, which does not simply reflect the solution-phase redox behavior of its monomers.

  20. Triply Halide-Bridged Dinuclear Iridium(III) Complexes with Chiral Diphosphine Ligands as New Easy-to-Handle Iridium Catalysts for Asymmetric Hydrogenation of Imines and N-Heteroaromatics. (United States)

    Mashima, Kazushi; Higashida, Kosuke; Iimuro, Atsuhiro; Nagae, Haruki; Kita, Yusuke


    Iridium(III) complexes bearing chiral ligands have proved to be active species in asymmetric hydrogenation of C=N bonds, though there are only a few iridium(III) precursors. We prepared triply halide-bridged dinuclear iridium complexes bearing chiral diphosphine ligands by simple treatment of the iridium(I) precursor, chiral diphosphine, and aqueous hydrogen halide. The strong advantage of these dinuclear iridium complexes is that they are air and moisture stable, leading to easy handling in asymmetric synthesis. The dinuclear iridium complexes exhibited high catalytic activity toward asymmetric hydrogenation of imines and N-heteroaromatics. Moreover, we demonstrated the application of triply halide-bridged dinuclear ruthenium(II) and rhodium(III) catalyst precursors for the asymmetric hydrogenation of ketonic substrates and simple olefins, respectively. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Iridium-catalyzed annulation of salicylimines with 1,3-dienes. (United States)

    Ebe, Yusuke; Nishimura, Takahiro


    Iridium-catalyzed annulation of salicylimines with 1,3-dienes gave high yields of the corresponding 4-aminochromanes with high stereoselectivity. The use of a chiral diene ligand enabled the asymmetric reaction to give 4-aminochromanes with high enantioselectivity.

  2. Low-Stress Iridium Coatings for Thin-Shell X-Ray Telescopes Project (United States)

    National Aeronautics and Space Administration — We propose to develop and commercialize a new type of low-stress iridium (Ir) X-ray mirror coating technology that can be used for the construction of...

  3. Synthesis and Thermal Decomposition Mechanism Study of a Novel Iridium Precursor

    Directory of Open Access Journals (Sweden)

    Yan Xin


    Full Text Available Ir(TFA3 (TFA=1,1,1-trifluoro-2,4-pentanedionate metal complexes with high purity was successfully synthesized. The metal complexes have been characterized by elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectroscopy. The volatility of metal complexes was studied by thermogravimetry analysis. And a possible decomposition mechanism was studied by mass spectroscopic analysis method. The novel iridium complexes can be severed as precursor in metalorganic chemical vapor deposition of iridium films. iridium films were deposited by metalorganic chemical vapor deposition method, and the Ir(TFA3 complex was used as precursor. The iridium thin films were characterized by X-ray diffraction and scanning electron microscopy in order to determine crystallinity and surface morphology.

  4. Iridium-Catalyzed Condensation of Primary Amines To Form Secondary Amines

    DEFF Research Database (Denmark)

    Lorentz-Petersen, Linda Luise Reeh; Jensen, Paw; Madsen, Robert


    Symmetric secondary amines are readily obtained by heating a neat primary amine with 0.5 mol% of bis(dichloro[eta(5)-pentamethylcyclopentadienyl]iridium). The products are isolated by direct distillation in good yields....

  5. Synthesis and luminescence properties of iridium(III) azide- and triazole-bisterpyridine complexes. (United States)

    Goldstein, Daniel C; Peterson, Joshua R; Cheng, Yuen Yap; Clady, Raphael G C; Schmidt, Timothy W; Thordarson, Pall


    We describe here the synthesis of azide-functionalised iridium(III) bisterpyridines using the "chemistry on the complex" strategy. The resulting azide-complexes are then used in the copper(I)-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition "click chemistry" reaction to from the corresponding triazole-functionalised iridium(III) bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III) bisterpyridines, but this effect can be reversed by the addition of copper(II) sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III) bisterpyridines can be functionalized for use in "click chemistry" facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

  6. Synthesis and characterization of low-valence actinide phosphide tellurides and ternary selenium-halide iridium complexes; Synthese und Charakterisierung niedervalenter Actinoidphosphidtelluride und ternaerer Selen-Halogenid-Komplexe des Iridiums

    Energy Technology Data Exchange (ETDEWEB)

    Stolze, Karoline


    The thesis on the synthesis and characterization of low-valence actinide phosphide tellurides and ternary selenium-halide iridium complexes includes two parts: a description of the experimental synthesis of UPTe and U2PTe2O and ThPTe and the synthesis of selenium-chloride iridium complexes and selenium-bromide iridium complexes. The characterization included X-ray diffraction and phase studies.

  7. Synthesis of Nanoporous Activated Iridium Oxide Films by Anodized Aluminum Oxide Templated Atomic Layer Deposition (United States)


    ABSTRACT 16. SECURITY CLASSIFICATION OF: Iridium oxide (IrOx) has been widely studied due to its applications in electrochromic devices , pH sensing, and...Title ABSTRACT Iridium oxide (IrOx) has been widely studied due to its applications in electrochromic devices , pH sensing, and neural stimulation...been widely studied due to its applications in electrochromic devices , pH sensing, and neural stimulation. Previous work has demonstrated that both

  8. Multidirectional Synthesis of Substituted Indazoles via Iridium-Catalyzed C-H Borylation. (United States)

    Sadler, Scott A; Hones, Andrew C; Roberts, Bryan; Blakemore, David; Marder, Todd B; Steel, Patrick G


    In the absence of a steric directing group, iridium-catalyzed C-H borylation of N-protected indazoles occurs rapidly and selectively at C-3 and the resulting boronate esters can be utilized in a range of downstream conversions. The functional group tolerance of the iridium-catalyzed C-H borylation reaction enables simple and efficient multidirectional syntheses of substituted indazoles to be realized.

  9. Enantiomeric separation of iridium (III) complexes using HPLC chiral stationary phases based on amylose derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hee Eun; Seo, Na Hyeon; Hyun, Myung Ho [Dept. of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Busan (Korea, Republic of)


    Cyclometalated iridium (III) complexes formed with three identical cyclometalating (C-N) ligands (homoleptic) or formed with two cyclometalating (C-N) ligands and one ancillary (LX) ligand (heteroleptic) have been known as highly phosphorescent materials and, thus, they have been utilized as efficient phosphorescent dopants in organic light emitting diodes (OLEDs) 1–3 or as effective phosphorescent chemosensors. 4–7 Cylometalated iridium (III) complexes are chiral compounds consisting of lambda (Λ, left-handed) and delta (Δ, right-handed) isomers. Racemic cyclometa- lated iridium (III) complexes emit light with no net polarization, but optically active cyclometalated iridium (III) complexes emit circularly polarized light. 8,9 Circularly polarized light can be used in various fields including highly efficient three dimensional electronic devices, photo nic devices for optical data storage, biological assays, and others. 8,9 In order to obtain optically active cylometalated iridium (III) complexes and to determine the enantiomeric composition of optically active cylometalated iridium (III) complexes, liquid chromatogr aphic enantiomer separation method on chiral stationary phases (CSPs) has been used. For example, Okamoto and coworkers first reported the high performance liquid chromatographic (HPLC) direct enantiomeric separation of two homoleptic cylometalated iridium (III) complexes on immobilized amylose tris(3,5- dimethylphenylcarbamate) (Chiralpak IA), coated cellulose tris(3,5-dimethylphenylcarbamate) (Chiralc el OD), and coated cellulose tris(4-methylbenzoate) (Chiralce l OJ). 10 Supercritical fluid chromatography (SFC) was also used by Bernhard and coworkers for the enantiomeric separation of cylometalated iridium (III) complexes on coated amylose tris(3,5-dimethylphenylcarbamate) (Chiralpak AD-H). 8 However, the general use of the HPLC method for the direct enantiomeric separation of homoleptic.

  10. Concepts for Cost-Effective Enhanced Cryosat Continuity: Opportunity in the Iridium PRIME Context (United States)

    Le Roy, Y.; Caubet, E.; Silverstrin, P.; Legrand, C.


    The Iridium-PRIME offer, recently initiated by the Iridium company, consists in hosting payloads on customized low cost Iridium-NEXT platforms on which the main telecom mission antenna (L-band) is removed. This leaves significant resources in terms of mass, volume and power consumption to host up to three payloads on these customized platforms. The Iridium-PRIME satellites will be inserted in the Iridium-NEXT constellation to take benefit of the low cost operation service (command, control and data telemetry through the life time of the Iridium-PRIME mission). Given the synergy between schedules of the Iridium-PRIME program (launches starting around 2020) and of a possible CryoSat Follow-On (FO) mission (launch around 2022) and the adequacy of the available on-board resources for such a mission, ESA tasked Thales Alenia Space, as responsible for the SIRAL radar instrument of the currently in-orbit CryoSat mission, to study the feasibility of a concept for enhanced continuity of CryoSat on an Iridium- PRIME satellite as potential low-cost fast-track solution. The study aimed to define a cost-effective topographic payload including not only the SIRAL radar but also the necessary sub-systems to retrieve the SIRAL antenna baseline attitude (star trackers) with high accuracy and to perform a Precise Orbit Determination (POD). All these aspects are presented in this paper. In addition, possible evolutions/improvements of the Ku-band radar instrument were analysed and are presented: adding a Ka-band nadir measurement capability and a Ku-band or Ka-band wide swath mode measurement capability. The transmission issue for the SIRAL science data is also discussed in the paper.

  11. Dynamic High-Temperature Characterization of an Iridium Alloy in Compression at High Strain Rates

    Energy Technology Data Exchange (ETDEWEB)

    Song, Bo [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Experimental Environment Simulation Dept.; Nelson, Kevin [Sandia National Lab. (SNL-CA), Livermore, CA (United States). Mechanics of Materials Dept.; Lipinski, Ronald J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Advanced Nuclear Fuel Cycle Technology Dept.; Bignell, John L. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Structural and Thermal Analysis Dept.; Ulrich, G. B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Radioisotope Power Systems Program; George, E. P. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Radioisotope Power Systems Program


    Iridium alloys have superior strength and ductility at elevated temperatures, making them useful as structural materials for certain high-temperature applications. However, experimental data on their high-temperature high-strain-rate performance are needed for understanding high-speed impacts in severe elevated-temperature environments. Kolsky bars (also called split Hopkinson bars) have been extensively employed for high-strain-rate characterization of materials at room temperature, but it has been challenging to adapt them for the measurement of dynamic properties at high temperatures. Current high-temperature Kolsky compression bar techniques are not capable of obtaining satisfactory high-temperature high-strain-rate stress-strain response of thin iridium specimens investigated in this study. We analyzed the difficulties encountered in high-temperature Kolsky compression bar testing of thin iridium alloy specimens. Appropriate modifications were made to the current high-temperature Kolsky compression bar technique to obtain reliable compressive stress-strain response of an iridium alloy at high strain rates (300 – 10000 s-1) and temperatures (750°C and 1030°C). Uncertainties in such high-temperature high-strain-rate experiments on thin iridium specimens were also analyzed. The compressive stress-strain response of the iridium alloy showed significant sensitivity to strain rate and temperature.

  12. High Iridium concentration of alkaline rocks of Deccan and implications to K/T boundary

    Indian Academy of Sciences (India)

    P N Shukla; N Bhandari; Anirban Das; A D Shukla; J S Ray


    We report here an unusually high concentration of iridium in some alkali basalts and alkaline rocks of Deccan region having an age of about 65Ma, similar to the age of the Cretaceous-Tertiary boundary. The alkali basalts of Anjar, in the western periphery of Deccan province, have irid-ium concentration as high as 178pg/g whereas the alkaline rocks and basalts associated with the Amba Dongar carbonatite complex have concentrations ranging between 8 and 80 pg/g. Some of these values are more than an order of magnitude higher than the concentration in the tholeiiticbasalts of Deccan, indicating the significance of alkaline magmatism in the iridium inventory at the Cretaceous-Tertiary boundary. Despite higher concentration, their contribution to the global inventory of iridium in the Cretaceous-Tertiary boundary clays remains small. The concentration of iridium in uorites from Amba Dongar was found to be < 30 pg/g indicating that iridium is not incorporated during their formation in hydrothermal activity.

  13. Iridium satellites help map electrical currents in space (United States)

    Showstack, Randy

    The satellite constellation of Iridium LLC, which filed for Chapter 11 bankruptcy in 1999 after it failed to win enough business for its commercial satellite communications services, is still orbiting at an altitude of about 780 kilometers. Now, however, the satellites are helping to write a new chapter in understanding space weather.Magnetometers onboard each of the system's 66 polar-orbiting satellites are working in conjunction with the high-frequency, multinational Super Dual Auroral Radar Network, or SuperDARN, to provide the first continuous measurements of electrical currents between Earth's upper atmosphere and space. These tools also are generating the first global maps of electrical power flowing into the polar upper atmosphere.

  14. Comparative modelling of chemical ordering in palladium-iridium nanoalloys

    Energy Technology Data Exchange (ETDEWEB)

    Davis, Jack B. A.; Johnston, Roy L., E-mail: [School of Chemistry, University of Birmingham, Birmingham B15 2TT (United Kingdom); Rubinovich, Leonid; Polak, Micha, E-mail: [Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva 84105 (Israel)


    Chemical ordering in “magic-number” palladium-iridium nanoalloys has been studied by means of density functional theory (DFT) computations, and compared to those obtained by the Free Energy Concentration Expansion Method (FCEM) using derived coordination dependent bond energy variations (CBEV), and by the Birmingham Cluster Genetic Algorithm using the Gupta potential. Several compositions have been studied for 38- and 79-atom particles as well as the site preference for a single Ir dopant atom in the 201-atom truncated octahedron (TO). The 79- and 38-atom nanoalloy homotops predicted for the TO by the FCEM/CBEV are shown to be, respectively, the global minima and competitive low energy minima. Significant reordering of minima predicted by the Gupta potential is seen after reoptimisation at the DFT level.

  15. The Electric Dipole Moment of Iridium Monosilicide, IrSi (United States)

    Le, Anh; Steimle, Timothy C.; Cheng, Lan; Stanton, John F.


    The optical spectrum of iridium monosilicide (IrSi) was recently observed using REMPI spectroscopy in the range 17200 to 23850 cm^{-1}. The observation was supported by an ab initio calculation which predicted a X^{2}Δ_{5/2} state. Here, we report on the analysis of the optical Stark effect for the X^{2}Δ_{5/2} and [16.0]1.5 (v=6) states. The (6,0)[16.0]1.5 - X^{2}Δ_{5/2} and the (7,0)[16.0]3.5- X^{2}Δ_{5/2} bands of IrSi have been recorded using high-resolution laser-induced fluorescence spectroscopy. The observed optical Stark shifts for the ^{193}IrSi and ^{191}IrSi isotopologues were analyzed to produce the electric dipole moments of -0.4139(64)D and 0.7821(63)D for the X^{2}Δ_{5/2} and [16.0]1.5 (v=6) states, respectively. The negative sign of electric dipole moment of the X^{2}Δ_{5/2} state is supported by high-level quantum-chemical calculations employing all-electron scalar-relativistic CCSD(T) method augmented with spin-orbit corrections as well as corrections due to full triple excitations. In particular, electron-correlation effects have been shown to be essential in the prediction of the negative sign of the dipole moment. A comparison with other iridium containing molecules will be made. Maria A. Garcia, Carolin Vietz, Fernando Ruipérez, Michael D. Morse, and Ivan Infante, Kimika Fakultatea, Euskal Herriko. J. Chem. Phys., (submitted)

  16. Iridium-Coated Rhenium Radiation-Cooled Rockets (United States)

    Reed, Brian D.; Biaglow, James A.; Schneider, Steven J.


    Radiation-cooled rockets are used for a range of low-thrust propulsion functions, including apogee insertion, attitude control, and repositioning of satellites, reaction control of launch vehicles, and primary propulsion for planetary space- craft. The key to high performance and long lifetimes for radiation-cooled rockets is the chamber temperature capability. The material system that is currently used for radiation-cooled rockets, a niobium alloy (C103) with a fused silica coating, has a maximum operating temperature of 1370 C. Temperature limitations of C103 rockets force the use of fuel film cooling, which degrades rocket performance and, in some cases, imposes a plume contamination issue from unburned fuel. A material system composed of a rhenium (Re) substrate and an iridium (Ir) coating has demonstrated operation at high temperatures (2200 C) and for long lifetimes (hours). The added thermal margin afforded by iridium-coated rhenium (Ir/Re) allows reduction or elimination of fuel film cooling. This, in turn, leads to higher performance and cleaner spacecraft environments. There are ongoing government- and industry-sponsored efforts to develop flight Ir/ Re engines, with the primary focus on 440-N, apogee insertion engines. Complementing these Ir/Re engine development efforts is a program to address specific concerns and fundamental characterization of the Ir/Re material system, including (1) development of Ir/Re rocket fabrication methods, (2) establishment of critical Re mechanical properly data, (3) development of reliable joining methods, and (4) characterization of Ir/Re life-limiting mechanisms.

  17. Coordination behavior of N-benzoylamino acids: Synthesis and structure of mixed-ligand complexes of palladium(Ⅱ) with N-benzoylamino acid dianion and diamine

    Institute of Scientific and Technical Information of China (English)

    龚钰秋; 陈耀峰; 顾建明; 胡秀荣


    Four new mixed-ligand complexes of pailadiumt(Ⅱ) with L1(N-benzoyl-α-amino acid dianion) and L2[ethyldiamine (en),2,2’-bipyridine (Bpy) and 1,10-phenanthroline (Phen)] were synthesized.Ail the complexes have been characterized by elemental analyses,molar conductance,infrared and 1H NMR spectra and therme-gravimetric analyses.Crystal structures of [Pd(Bpy)(Bzval-N,O)] and [Pd(en) (Bzphe-N,O)] H2O have been do termmed by X-ray diffraction analysis.The results indicate that in all the complexes hgand L1 coordinates to palladium (Ⅱ) through deprotonated amide nitrogen and carboxylic oxygen,and there are some intramolecular nonrovalent in teractions in the complexes.

  18. Radiomenolysis of the endometrium by high-dose iridium-192 irradiation- clinical and cytomorphologic results

    Energy Technology Data Exchange (ETDEWEB)

    Kucera, H.; Huber, H.; Weghaupt, K.


    423 patients with benign recurrent uterine bleeding resistant to other therapy were treated by intracavitary radiotherapy. In all cases there was a contraindication for the operative removal of the uterus. Since 1980 radiomenolysis was performed by high-dose Iridium-192 irradiation (afterloading technique). In 94.3% of our cases with Radium-226 irradiation the bleeding could be treated successfully. Side effects of the irradiation occurred only in a minimal and neglectible percentage. In all cases irradiated with Iridium-192 the bleeding stopped after treatment. Side effects could not be observed. Therefore the intrauterine contact-irradiation therapy with high-dose Iridium-192 should be remembered in cases of uterine bleeding resistant to hormonal therapy or in cases of high risk for operation. With the afterloading device the molestation for the patients could be reduced to a minimum. By intrauterine exfoliative smear performed before and after irradiation the cytomorphologic effect of an Iridium-192 afterloading irradiation was demonstrated. The examinations showed that the cytologic findings were characteristic for the effect if ionizing radiation of the histologically unchanged, not radiosensitive, normal cylindrical epithelium. A marked cellular diathesis and augmentation of size of nuclei and plasma is a characteristic result of the irradiation with Iridium-192.

  19. Electrodeposition of platinum-iridium alloy nanowires for hermetic packaging of microelectronics. (United States)

    Petrossians, Artin; Whalen, John J; Weiland, James D; Mansfeld, Florian


    An electrodeposition technique was applied for fabrication of dense platinum-iridium alloy nanowires as interconnect structures in hermetic microelectronic packaging to be used in implantable devices. Vertically aligned arrays of platinum-iridium alloy nanowires with controllable length and a diameter of about 200 nm were fabricated using a cyclic potential technique from a novel electrodeposition bath in nanoporous aluminum oxide templates. Ti/Au thin films were sputter deposited on one side of the alumina membranes to form a base material for electrodeposition. Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) were used to characterize the morphology and the chemical composition of the nanowires, respectively. SEM micrographs revealed that the electrodeposited nanowires have dense and compact structures. EDS analysis showed a 60:40% platinum-iridium nanowire composition. Deposition rates were estimated by determining nanowire length as a function of deposition time. High Resolution Transmission Electron Microscopy (HRTEM) images revealed that the nanowires have a nanocrystalline structure with grain sizes ranging from 3 nm to 5 nm. Helium leak tests performed using a helium leak detector showed leak rates as low as 1 × 10(-11) mbar L s(-1) indicating that dense nanowires were electrodeposited inside the nanoporous membranes. Comparison of electrical measurements on platinum and platinum-iridium nanowires revealed that platinum-iridium nanowires have improved electrical conductivity.

  20. Effect of iridium loading on HZSM-5 for isomerization of n-heptane

    Institute of Scientific and Technical Information of China (English)

    Herma Dina Setiabudi; Sugeng Triwahyono; Aishah Abdul Jalil; Nur Hidayatul Nazirah Kamarudin; Muhammad Arif Ab Aziz


    The effect of iridium loading on the properties and catalytic isomerization of n-heptane over Ir-HZSM-5 is studied.Ir-HZSM-5 was prepared by impregnation method and subjected to isomerization process in the presence of flowing hydrogen gas.XRD and BET studies show that the presence of iridium stabilizes the crystalline structure of HZSM-5,leading to more ordered framework structure and larger surface area.TGA and FTIR results substantiate that iridium species interacts with OH group on the surface of HZSM-5.Pyridine FT-IR study verifies the interaction between iridium and surface OH group slightly increased the Br(o)nsted and Lewis acid sites without changing the lattice structure of HZSM-5.The presence of iridium and the increase of strong Lewis acid sites on HZSM-5 were found to bring an increase about 4.1%,33.2% and 11.8% in conversion,selectivity and yield of n-heptane isomerization,respectively.

  1. Luminescent Iridium(III) Complex Labeled DNA for Graphene Oxide-Based Biosensors. (United States)

    Zhao, Qingcheng; Zhou, Yuyang; Li, Yingying; Gu, Wei; Zhang, Qi; Liu, Jian


    There has been growing interest in utilizing highly photostable iridium(III) complexes as new luminescent probes for biotechnology and life science. Herein, iridium(III) complex with carboxyl group was synthesized and activated with N-hydroxysuccinimide, followed by tagging to the amino terminate of single-stranded DNA (ssDNA). The Ir-ssDNA probe was further combined with graphene oxide (GO) nanosheets to develop a GO-based biosensor for target ssDNA detection. The quenching efficiency of GO, and the photostability of iridium(III) complex and GO-Ir-ssDNA biosensor, were also investigated. On the basis of the high luminescence quenching efficiency of GO toward iridium(III) complex, the GO-Ir-ssDNA biosensor exhibited minimal background signals, while strong emission was observed when Ir-ssDNA desorbed from GO nanosheets and formed a double helix with the specific target, leading to a high signal-to-background ratio. Moreover, it was found that luminescent intensities of iridium(III) complex and GO-Ir-ssDNA biosensor were around 15 and 3 times higher than those of the traditional carboxyl fluorescein (FAM) dye and the GO-FAM-ssDNA biosensor after UV irradiation, respectively. Our study suggested the sensitive and selective Ir-ssDNA probe was suitable for the development of highly photostable GO-based detection platforms, showing promise for application beyond the OLED (organic light emitting diode) area.

  2. Iridium profiles and delivery across the Cretaceous/Paleogene boundary (United States)

    Esmeray-Senlet, Selen; Miller, Kenneth G.; Sherrell, Robert M.; Senlet, Turgay; Vellekoop, Johan; Brinkhuis, Henk


    We examined iridium (Ir) anomalies at the Cretaceous/Paleogene (K/Pg) boundary in siliciclastic shallow marine cores of the New Jersey Coastal Plain, USA, that were deposited at an intermediate distance (∼2500 km) from the Chicxulub, Mexico crater. Although closely spaced and generally biostratigraphically complete, the cores show heterogeneity in terms of preservation of the ejecta layers, maximum concentration of Ir measured (∼0.1-2.4 ppb), and total thickness of the Ir-enriched interval (11-119 cm). We analyzed the shape of the Ir profiles with a Lagrangian particle-tracking model of sediment mixing. Fits between the mixing model and measured Ir profiles, as well as visible burrows in the cores, show that the shape of the Ir profiles was determined primarily by sediment mixing via bioturbation. In contrast, Tighe Park 1 and Bass River cores show post-depositional remobilization of Ir by geochemical processes. There is a strong inverse relationship between the maximum concentration of Ir measured and the thickness of the sediments over which Ir is spread. We show that the depth-integrated Ir inventory is similar in the majority of the cores, indicating that the total Ir delivery at time of the K/Pg event was spatially homogeneous over this region. Though delivered through a near-instantaneous source, stratospheric dispersal, and settling, our study shows that non-uniform Ir profiles develop due to changes in the regional delivery and post-depositional modification by bioturbation and geochemical processes.

  3. Selective Hydrogenation of Avermectin Catalyzed by Iridium-Phosphine Complexes

    Institute of Scientific and Technical Information of China (English)

    MA, Xiao-Yan; WANG, Kun; ZHANG, Lei; LI, Xian-Jun; LI, Rui-Xiang


    A series of new iridium complexes, IrCl(COD)(TMOPP) (1) [COD=1,5-cyclooctadiene, TMOPP=tris(4-methoxyphenyl)phosphine], IrCl(COD)(TFMPP) (2) [TFMPP = tris(4-trifluoromethylphenyl)phosphine], IrCl-(COD)(BDNA) (3) [BDNA=1,8-bis(diphenylphosphinomethyl)naphthalene], IrCl(COD)(BISBI) (4) [BISBI=2,2'-bis(diphenylphosphinomethyl)biphenyl] and IrCl(COD)(BDPB) (5) [BDPB = 1,2-bis(diphenylphosphinomethyl)benzene], were synthesized and characterized by NMR spectra and elemental analyses. In order to obtain the relationships between complex structures and their catalytic properties, IrCl(COD)(DPPM) (6) [DPPM=bis(diphenylphosphino)methane], IrCl(COD)(DPPE) (7) [DPPE= 1,2-bis(diphenylphosphino)ethane], IrCl(COD)-(DPPP) (8) [DPPP=1,3-bis(diphenylphosphino)propane] and IrCl(COD)(TPP) (9) [TPP=triphenylphosphine],were also synthesized according to the reported methods. The hydrogenation results showed that the low electronic density at the central metal was favorable to increase the catalytic activity for the hydrogenation of avermectin, but decrease the selectivity to ivermectin. The complex with a large chelating ring and a bulky chelating backbone would easily cause the cleavage of C-O bond in avermectin to give a byproduct avermectin aglycon.

  4. Early stages of diamond BEN-HFCVD on iridium

    Energy Technology Data Exchange (ETDEWEB)

    Arnault, J.C.; Faerber, J. [Groupe Surfaces-Interfaces, Institut de Physique et Chimie de Strasbourg, IPCMS-GSI, UMR 7504, BP 43, 23, rue du Loess, 67034 Strasbourg Cedex 2 (France); Vonau, F. [Laboratoire de Physique et Spectroscopie Electronique, 4, rue des Freres Lumiere, 68093 Mulhouse Cedex (France); Arabski, J.; Schmerber, G. [Groupe des Materiaux Metalliques, IPCMS-GEMM, 91404 Orsay (France); Wyczisk, F.; Legagneux, P. [Thales R and T, Domaine de Corbeville, 91404 Orsay Cedex (France)


    This study attempts to better understand the BEN effects on diamond nucleation on iridium buffer layers investigated by in situ electron spectroscopies (XPS, AES). The surface morphology is further characterised by AFM and SEM FEG. Nano-Auger experiments provide information about the chemical nature of the crystals. During the early stages of BEN, nano-Auger observations revealed a significant carbon sp{sup 3} contribution within the bright crystals whereas the surrounding areas are mainly sp{sup 2}. This emphasizes the BEN effect on the diamond nucleation. Moreover, AES experiments reveal the formation of graphite. The equivalent thickness of the graphite layer is estimated from XPS data, it is close to a monolayer. The graphite formation is not a proper effect of BEN because it is also obtained under CVD environment according to our study. Anisotrope crystals arranged along left angle 110 right angle directions have been characterized by HR-SEM and AFM. (copyright 2003 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  5. Cytologic modifications in the endometrium after high-dose iridium-192 irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Huber, H.; Knogler, W.; Kucera, H.; Ulm, R.


    By intrauterine exfoliative smear performed twice in each of seventeen patients, the cytomorphologic effect of an iridium-192 after-loading irradiation was demonstrated. The examinations showed that the cytologic findings were characteristic of the effect of ionizing radiation even in case of the histologically unchanged, not radiosensitive cylindrical epithelium. After the iridium irradiation of malignantly transformed cells of the cylindrical epithelium with 1000 rd, vacuolation and pseudoeosinophilia were the predominant lesions, while after 2000 rd this was above all the presence of macronucleoli. A marked cellular diathesis is a characteristic result of the irradiation with iridium-192. Although hyperchromasia is not an absolute sign of malignancy in case of the adenocarcinoma, it should be mentioned that chromatin concentrations are scarcely found after irradiation.

  6. C-H activation of ethers by pyridine tethered PCsp3P-type iridium complexes. (United States)

    Cui, Peng; Babbini, Dominic C; Iluc, Vlad M


    Iridium PCsp3P complexes featuring a novel bis(2-diphenylphosphinophenyl)-2-pyridylmethane ligand (PC(Py)HP) are reported. C-H activation reactions between the dihydride complex [(PC(Py)P)Ir(H)2] and tetrahydrofuran or methyl tert-butyl ether in the presence of a hydrogen acceptor, norbornene (NBE), at ambient temperature led exclusively to the hydrido oxyalkyl complexes, [(PC(Py)P)IrH(C4H7O)] and [(PC(Py)P)IrH(CH2O(t)Bu)], respectively. The internal pyridine donor is important and stabilizes these species by coordination to the iridium center. The coordination of pyridine to the iridium center is labile, however, and its dissociation occurs in the presence of a suitable substrate, as demonstrated by the intramolecular nucleophilic attack of pyridine on a vinylidene intermediate generated from PhC[triple bond, length as m-dash]CH.

  7. Sputtered platinum-iridium layers as electrode material for functional electrostimulation

    Energy Technology Data Exchange (ETDEWEB)

    Ganske, G., E-mail: ganske@iwe1.rwth-aachen.d [Institute of Materials in Electrical Engineering I, RWTH Aachen University, Sommerfeldstr. 24, D-52074 Aachen (Germany); Slavcheva, E. [Institute of Materials in Electrical Engineering I, RWTH Aachen University, Sommerfeldstr. 24, D-52074 Aachen (Germany); Institute of Electrochemistry and Energy Systems, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Ooyen, A. van; Mokwa, W.; Schnakenberg, U. [Institute of Materials in Electrical Engineering I, RWTH Aachen University, Sommerfeldstr. 24, D-52074 Aachen (Germany)


    In this study co-sputtered layers of platinum-iridium (PtIr) are investigated as stimulation electrode material. The effects of different sputter parameters on the morphology and the electrochemical behavior are examined. It is shown that films sputtered at the lowest incident energy possess the highest charge storage capacity (CSC). At a Pt:Ir atomic-ratio of 55:45 the obtained CSC of 22 mC/cm{sup 2} is enhanced compared to the standard stimulation material platinum (16 mC/cm{sup 2}) but inferior to iridium which has a CSC of 35 mC/cm{sup 2}. Long term cyclic voltammetry measurements show that PtIr can be activated which increases the CSC to 29 mC/cm{sup 2}. Also a change in the film morphology is observed. Sputtered platinum-iridium films promise to combine high mechanical strength and increased charge storage capacity.

  8. Properties of mixed molybdenum oxide iridium oxide thin films synthesized by spray pyrolysis (United States)

    Patil, P. S.; Kawar, R. K.; Sadale, S. B.; Inamdar, A. I.; Deshmukh, H. P.


    Molybdenum-doped iridium oxide thin films have been deposited onto corning glass- and fluorine-doped tin oxide coated corning glass substrates at 350 °C by using a pneumatic spray pyrolysis technique. An aqueous solution of 0.01 M ammonium molybdate was mixed with 0.01 M iridium trichloride solution in different volume proportions and the resultant solution was used as a precursor solution for spraying. The as-deposited samples were annealed at 600 °C in air medium for 1 h. The structural, electrical and optical properties of as-deposited and annealed Mo-doped iridium oxide were studied and values of room temperature electrical resistivity, and thermoelectric power were estimated. The as-deposited samples with 2% Mo doping exhibit more pronounced electrochromism than other samples, including pristine Ir oxide.

  9. Oxygen atom transfer to a half-sandwich iridium complex: clean oxidation yielding a molecular product. (United States)

    Turlington, Christopher R; White, Peter S; Brookhart, Maurice; Templeton, Joseph L


    The oxidation of [Ir(Cp*)(phpy)(NCAr(F))][B(Ar(F))4] (1; Cp* = η(5)-pentamethylcyclopentadienyl, phpy = 2-phenylene-κC(1')-pyridine-κN, NCAr(F) = 3,5-bis(trifluoromethyl)benzonitrile, B(Ar(F))4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) with the oxygen atom transfer (OAT) reagent 2-tert-butylsulfonyliodosobenzene (sPhIO) yielded a single, molecular product at -40 °C. New Ir(Cp*) complexes with bidentate ligands derived by oxidation of phpy were synthesized to model possible products resulting from oxygen atom insertion into the iridium-carbon and/or iridium-nitrogen bonds of phpy. These new ligands were either cleaved from iridium by water or formed unreactive, phenoxide-bridged iridium dimers. The reactivity of these molecules suggested possible decomposition pathways of Ir(Cp*)-based water oxidation catalysts with bidentate ligands that are susceptible to oxidation. Monitoring the [Ir(Cp*)(phpy)(NCAr(F))](+) oxidation reaction by low-temperature NMR techniques revealed that the reaction involved two separate OAT events. An intermediate was detected, synthesized independently with trapping ligands, and characterized. The first oxidation step involves direct attack of the sPhIO oxidant on the carbon of the coordinated nitrile ligand. Oxygen atom transfer to carbon, followed by insertion into the iridium-carbon bond of phpy, formed a coordinated organic amide. A second oxygen atom transfer generated an unidentified iridium species (the "oxidized complex"). In the presence of triphenylphosphine, the "oxidized complex" proved capable of transferring one oxygen atom to phosphine, generating phosphine oxide and forming an Ir-PPh3 adduct in 92% yield. The final Ir-PPh3 product was fully characterized.

  10. The Allyl Intermediate in Regioselective and Enantioselective Iridium-Catalyzed Asymmetric Allylic Substitution Reactions


    Madrahimov, Sherzod T.; Markovic, Dean; Hartwig, John F.


    The isolation and structural characterization of metallacyclic allyl (2a) and crotyl (2b) iridium complexes are reported. Complexes 2a and 2b are rare examples of iriduim allyl complexes that undergo nucleophilic attack at terminal position, rather than the central position, of the allyl unit. Structures of 2a and 2b were obtained by X-ray diffraction. Nucleophilic attack was observed at the carbon that is bound to iridium trans to phosphorus through a longer Ir-C bond. However, the effect of...

  11. Experimental and Theoretical Mechanistic Investigation of the Iridium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Singh, Thishana; Harris, Pernille


    cycles. One carbon monoxide ligand was shown to remain coordinated to iridium throughout the reaction, and release of carbon monoxide was suggested to occur from a dicarbonyl complex. IrH2Cl(CO)(rac-BINAP) was also synthesized and detected in the dehydrogenation of benzyl alcohol. In the same experiment......The mechanism for the iridium-BINAP catalyzed dehydrogenative decarbonylation of primary alcohols with the liberation of molecular hydrogen and carbon monoxide was studied experimentally and computationally. The reaction takes place by tandem catalysis through two catalytic cycles involving...

  12. ARTICLES: Microwave Assisted Synthesis of a New Triplet Iridium(III) Pyrazine Complex (United States)

    Wu, Qiu-hua; Wang, Chuan-hong; Song, Xi-ming; Zhang, Guo-lin


    A new cyclometalated iridium(III) complex Ir(DPP)3 (DPP = 2,3-diphenylpyrazine) was prepared by reaction of DPP with iridium trichloride hydrate under microwave irradiation. The structure of the complex was confirmed by elemental analysis, 1H NMR, and mass spectroscopy. The UV-Vis absorption and photoluminescent properties of the complex were investigated. The complex shows strong 1MLCT (singlet metal to ligand charge-transfer) and 3MLCT (triplet metal to ligand charge-transfer) absorption at 382 and 504 nm, respectively. The complex also shows strong photoluminescence at 573 nm at room temperature. These results suggest the complex to be a promising phosphorescent material.

  13. Synthesis of Fluoroalkoxy Substituted Arylboronic Esters by Iridium-Catalyzed Aromatic C–H Borylation

    KAUST Repository

    Batool, Farhat


    The preparation of fluoroalkoxy arylboronic esters by iridium-catalyzed aromatic C–H borylation is described. The fluoroalkoxy groups employed include trifluoromethoxy, difluoromethoxy, 1,1,2,2-tetrafluoroethoxy, and 2,2-difluoro-1,3-benzodioxole. The borylation reactions were carried out neat without the use of a glovebox or Schlenk line. The regioselectivities available through the iridium-catalyzed C–H borylation are complementary to those obtained by the electrophilic aromatic substitution reactions of fluoroalkoxy arenes. Fluoroalkoxy arylboronic esters can serve as versatile building blocks.

  14. Influence of iridium on the reactivity of LaFeO3 base perovskites

    DEFF Research Database (Denmark)

    Kindermann, L.; Das, D.; Bahadur, D.


    The influence of iridium on the reactivity of powder mixtures made of perovskites and 8 mol% yttria stabilized zirconia (8 YSZ) is reported. Iridium is added to the perovskites of the composition (La0.6M0.4)(z)Fe0.8TM0.2O3-delta (M = Sr, Ca; TM = Mn, Co; z = 0.90, 1.00) via the gaseous phase. Iri...... of the perovskites, thermodynamic activities, Ir(IV)-O bonding, tolerance factor and oxygen migration....

  15. Study of the lithiated phenylacetonitrile monoanions and dianions formed according to the lithiated base used (LHMDS, LDA, or n-BuLi). 2. Alkylation and deuteriation mechanism study by vibrational and NMR spectroscopy and quantum chemistry calculations. (United States)

    Strzalko, Tekla; Wartski, Lya; Corset, Jacques; Castellà-Ventura, Martine; Froment, Françoise


    Mechanisms of alkylation by PhCH(2)Cl or CH(3)I in THF and of deuteriation by DCl (4 N in D(2)O) in THF or THF-toluene of lithiated phenylacetonitrile monoanions and dianions obtained with LHMDS, LDA, or n-BuLi are studied by vibrational and NMR spectroscopy and quantum chemistry calculations. Dialkylation of the three dilithio dianions generated with n-BuLi (2.0-2.7 equiv, THF-hexane) depends on their structure: N-lithio (PhCCNLi)(-)Li(+) and (C,N)-dilithio PhCLiCNLi dianions afford PhCR(2)CN (R = PhCH(2), CH(3)) from the intermediate N-lithio monoalkylated monoanion PhCRCNLi 10; C-lithio dianion (PhCLiCN)(-)Li(+) leads to a carbenoid species, the C-lithio monoalkylated nitrile PhCLiRCN 11, which either eliminates carbene Ph-C-R and different LiCN species or isomerizes to PhCRCNLi in the presence of LiX (X = Cl, I). Dialkylation or dideuteriation of monoanions (monomers, dimers, and heterodimers [PhCHCNLi·LiR'], R' = (SiMe(3))(2)N, (i-Pr)(2)N) obtained with LHMDS or LDA (2.4 equiv, THF) proceeds via a sequential mechanism involving monometalation-monoalkylation (or monodeuteriation) reactions. Some carbene and (LiCNLi)(+) are also observed, and explained by another mechanism implying the C-lithio monoalkylated monoanion PhCLiRCN 9 in the presence of LiX. These results show the ambiphilic behavior of PhCLiRCN as a carbenoid (11) or a carbanion (9) and the importance of LiX formed in situ in the first alkylation step.

  16. High Strain Rate Testing of Welded DOP-26 Iridium

    Energy Technology Data Exchange (ETDEWEB)

    Schneibel, J. H. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Miller, R. G. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Carmichael, C. A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Fox, E. E. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Ulrich, G. B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); George, E. P. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)


    The iridium alloy DOP-26 is used to produce Clad Vent Set cups that protect the radioactive fuel in radioisotope thermoelectric generators (RTGs) which provide electric power for spacecraft and rovers. In a previous study, the tensile properties of DOP-26 were measured over a wide range of strain rates and temperatures and reported in ORNL/TM-2007/81. While that study established the properties of the base material, the fabrication of the heat sources requires welding, and the mechanical properties of welded DOP-26 have not been extensively characterized in the past. Therefore, this study was undertaken to determine the mechanical properties of DOP-26 specimens containing a transverse weld in the center of their gage sections. Tensile tests were performed at room temperature, 750, 900, and 1090°C and engineering strain rates of 1×10-3 and 10 s-1. Room temperature testing was performed in air, while testing at elevated temperatures was performed in a vacuum better than 1×10-4 Torr. The welded specimens had a significantly higher yield stress, by up to a factor of ~2, than the non-welded base material. The yield stress did not depend on the strain rate except at 1090°C, where it was slightly higher for the faster strain rate. The ultimate tensile stress, on the other hand, was significantly higher for the faster strain rate at temperatures of 750°C and above. At 750°C and above, the specimens deformed at 1×10-3 s-1 showed pronounced necking resulting sometimes in perfect chisel-edge fracture. The specimens deformed at 10 s-1 exhibited this fracture behavior only at the highest test temperature, 1090°C. Fracture occurred usually in the fusion zone of the weld and was, in most cases, primarily intergranular.

  17. Comparative study of the hydration systems formed during interactions of hydrogen phosphate dianions with putrescine, nor-putrescine and magnesium dications (United States)

    Figlerowicz, M.; Utzig, E.; Alejska, M.; Bratek-Wiewiórowska, M. D.; Wiewiórowski, M.


    A comparative study of hydration systems, formed as a result of the interaction between hydrogen phosphate dianions and three naturally occurring cations (putrescine (Put), its nor-homologue (nPut) and magnesium), is presented. On the basis of X-ray data and IR, NMR and calorimetric measurements, we have determined how the structure and physicochemical properties of the cations influence the system of phosphate residue hydration. Our study demonstrates that the stability of the hydration systems depends not only on the character of the bonds used by water to link with other salt components (coordinate or hydrogen bonds), but also on the location of the water molecules in the crystal lattice. In addition, contrary to magnesium salts, the dehydration of diamine (Put and nPut) hydrogen phosphates is reversible. Both dehydration and rehydration processes take place in the solid state. During rehydration, the crystalline anhydrous salt absorbs water molecules from the atmosphere. This leads to the reconstruction of the hydrated salt structure; this means that the salt which is the product of rehydration is identical with that obtained by crystallization from water solution.

  18. Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion (United States)

    Winghart, Marc-Oliver; Yang, Ji-Ping; Vonderach, Matthias; Unterreiner, Andreas-Neil; Huang, Dao-Ling; Wang, Lai-Sheng; Kruppa, Sebastian; Riehn, Christoph; Kappes, Manfred M.


    Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt2(μ-P2O5H2)4 + 2H]2- after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet 1A2u state and concomitant rise in population of the triplet 3A2u state, via sub-picosecond intersystem crossing (ISC). We find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet 1A2u state takes only a few picoseconds, ESETD from the triplet 3A2u state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt2(μ-P2O5H2)4 + 2H]2- is the first example of a photoexcited multianion for which ESETD has been observed following ISC.

  19. Ytterbocenes as one- and two-electron reductants in their reactions with diazadienes: YbIII mixed-ligand bent-sandwich complexes containing a dianion of diazabutadiene. (United States)

    Trifonov, Alexander A; Borovkov, Ivan A; Fedorova, Elena A; Fukin, Georgii K; Larionova, Joulia; Druzhkov, Nikolai O; Cherkasov, Vladimir K


    Ytterbocene [Yb(C(5)MeH(4))(2)(thf)(2)] reacts with diazabutadiene 2,6-iPr(2)C(6)H(3)-N=CH-CH=N-C(6)H(3)iPr(2)-2,6 (DAD) as a one-electron reductant to afford a bis(cyclopentadienyl) Yb(III) derivative containing a DAD radical anion [Yb(C(5)MeH(4))(2)(dad(-.))]. However, ytterbocenes [YbCp*(2)(thf)(2)] (Cp*=C(5)Me(5), C(5)Me(4)H) coordinated by sterically demanding cyclopentadienyl ligands act as two-electron reductants in their reactions with DAD. These reactions occur by abstraction of one Cp* ring and result in the formation of novel Yb(III) mixed-ligand bent-sandwich complexes, [YbCp*(dad)(thf)], in which the dianion of DAD has an uncommon terminal eta(4)-coordination to the ytterbium atom. The variable-temperature magnetic measurements of complex [Yb(C(5)Me(5))(dad)(thf)] suggest the existence of redox tautomerism for this compound.

  20. Synthesis and Crystal Structure of [ 1- (4' -fluorobenzyl )pyridinium ]2 [ Ni (dto)2 ] Complex(dto2- = dithiooxalate dianion)%配合物[1-(4'-fluorobenzyl)pyridinium]2[Ni(dto)2](dto2-=dithiooxalate dianion)的合成及晶体结构

    Institute of Scientific and Technical Information of China (English)

    刘玲; 谢景力; 任小明; 孟庆金


    The complex [ 1- (4'-fluorobenzyl) pyridinium ] 2 [ Ni (dto) 2 ] (dto2 - means dithiooxalate dianion) has been pre-pared by reaction of Na2[Ni(S2C2O2)2] and the 1-(4'-fluorobenzyl) pyridinium chloride salt. The crystallographicdata for the title complex: triclinic P1, a =8. 5698(8) A, b =9. 3461(9) A, c = 10. 5361(10) A, α =67. 177(2)°, β =67.398(2)°, γ =79. 611(2)°, V=717.59(12) A3, Z= 1. The [Ni(dto) 2] 2- anion with the Ni atomO is clearly observed. The nature and size of cation seems to play an important factor in the type of intermolecularinteractions as well as the crystal packing in this kind of complexes.

  1. Iridium(I) Compounds as Prospective Anticancer Agents: Solution Chemistry, Antiproliferative Profiles and Protein Interactions for a Series of Iridium(I) N-Heterocyclic Carbene Complexes. (United States)

    Gothe, Yvonne; Marzo, Tiziano; Messori, Luigi; Metzler-Nolte, Nils


    A series of structurally related mono- and bis-NHC-iridium(I) (NHC: N-heterocyclic carbene) complexes have been investigated for their suitability as potential anticancer drugs. Their spectral behaviour in aqueous buffers under physiological-like conditions and their cytotoxicity against the cancer cell lines MCF-7 and HT-29 are reported. Notably, almost all complexes exhibit significant cytotoxic effects towards both cancer cell lines. In general, the cationic bis-carbene complexes show higher stability and greater anticancer activity than their neutral mono-carbene analogues with IC50 values in the high nanomolar range. Furthermore, to gain initial mechanistic insight, the interactions of these iridium(I)-NHC complexes with two model proteins, namely lysozyme and cytochrome c, were explored by HR-ESI-MS analyses. The different protein metalation patterns of the complexes can be roughly classified into two distinct groups. Those interactions give us a first idea about the possible mechanism of action of this class of compounds. Overall, our findings show that iridium(I)-NHC complexes represent very interesting candidates for further development as new metal-based anticancer drugs.

  2. High temperature reactive ion etching of iridium thin films with aluminum mask in CF4/O2/Ar plasma

    Directory of Open Access Journals (Sweden)

    Chia-Pin Yeh


    Full Text Available Reactive ion etching (RIE technology for iridium with CF4/O2/Ar gas mixtures and aluminum mask at high temperatures up to 350 °C was developed. The influence of various process parameters such as gas mixing ratio and substrate temperature on the etch rate was studied in order to find optimal process conditions. The surface of the samples after etching was found to be clean under SEM inspection. It was also shown that the etch rate of iridium could be enhanced at higher process temperature and, at the same time, very high etching selectivity between aluminum etching mask and iridium could be achieved.

  3. Asymmetric hydrogenation of quinolines catalyzed by iridium complexes of monodentate BINOL-derived phosphoramidites

    NARCIS (Netherlands)

    Mrsic, Natasa; Lefort, Laurent; Boogers, Jeroen A. F.; Minnaard, Adriaan J.; Feringa, Ben L.; de Vries, Johannes G.; Mršić, Nataša

    The monodentate BINOL-derived phosphoramidite PipPhos is used as ligand for the iridium-catalyzed asymmetric hydrogenation of 2- and 2,6-substituted quinolines. If tri-ortho-tolylphosphine and/or chloride salts are used as additives enantioselectivities are strongly enhanced up to 89%. NMR indicates

  4. Asymmetric synthesis of N,O-heterocycles via enantioselective iridium-catalysed intramolecular allylic amidation

    NARCIS (Netherlands)

    Zhao, Depeng; Fananas-Mastral, Martin; Chang, Mu-Chieh; Otten, Edwin; Feringa, Ben L.


    Chiral N,O-heterocycles were synthesized in high yields and excellent enantioselectivity up to 97% ee via iridium-catalysed intramolecular allylic substitution with nucleophilic attack by the amide oxygen atom. The resulting benzoxazine derivatives were further transformed into challenging chiral

  5. The allyl intermediate in regioselective and enantioselective iridium-catalyzed asymmetric allylic substitution reactions. (United States)

    Madrahimov, Sherzod T; Markovic, Dean; Hartwig, John F


    The isolation and structural characterization of metallacyclic allyl (2a) and crotyl (2b) iridium complexes are reported. Complexes 2a and 2b are rare examples of iriduim allyl complexes that undergo nucleophilic attack at terminal position, rather than the central position, of the allyl unit. Structures of 2a and 2b were obtained by X-ray diffraction. Nucleophilic attack was observed at the carbon that is bound to iridium trans to phosphorus through a longer Ir-C bond. However, the effect of the trans phosphine ligand on the Ir-C bond lengths was smaller than the effect of the substituent on the allyl group in 2b. The competence of complexes 2a and 2b to be intermediates in the catalytic asymmetric allylic substitutions was evaluated by studying their reactivity toward stabilized carbon and heteroatom nucleophiles and comparing the rates and selectivities to those of the catalytic reactions. The stereoselectivity and regioselectivity of stoichiometric reactions of 2b were similar to those of reactions catalyzed by the previously reported iridium catalysts, supporting their intermediacy in the catalytic reactions. On the basis of the structural data, a model is proposed for the origin of stereoselectivity in iridium-catalyzed asymmetric allylic substitution reactions.

  6. Asymmetric Cyclization of N-Sulfonyl Alkenyl Amides Catalyzed by Iridium/Chiral Diene Complexes. (United States)

    Nagamoto, Midori; Yanagi, Tomoyuki; Nishimura, Takahiro; Yorimitsu, Hideki


    Iridium/chiral diene complexes efficiently catalyzed the asymmetric cyclization of N-sulfonyl alkenyl amides to give the corresponding 2-pyrrolidone derivatives with high enantioselectivity. A mechanistic study revealed that the reaction proceeds via nucleophilic attack of the amide on the alkene moiety.

  7. Report of Iridium/{sup 238}PuO{sub 2} Compatibility Test

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, D.H.


    This study indicates that the chemical purity of the fuel used presently to fabricate fueled clad vent sets will not present any special problems to the performance of the fueled clad vent sets as intended. However, cation impurities in the fuel can have a deleterious effect on the iridium cladding and vents and should be minimized as much as practical.

  8. Iridium complexes of new NCP pincer ligands: catalytic alkane dehydrogenation and alkene isomerization. (United States)

    Jia, Xiangqing; Zhang, Lei; Qin, Chuan; Leng, Xuebing; Huang, Zheng


    Iridium complexes of novel NCP pincer ligands containing pyridine and phosphinite arms have been synthesized. One Ir complex shows good catalytic activity for alkane dehydrogenation, and all complexes are highly active for olefin isomerization. A combination of the Ir complex and a (PNN)Fe pincer complex catalyzes the formation of linear alkylboronates selectively from internal olefins via sequential olefin isomerization-hydroboration.

  9. Experimental and Theoretical Mechanistic Investigation of the Iridium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Singh, Thishana; Harris, Pernille;


    The mechanism for the iridium-BINAP catalyzed dehydrogenative decarbonylation of primary alcohols with the liberation of molecular hydrogen and carbon monoxide was studied experimentally and computationally. The reaction takes place by tandem catalysis through two catalytic cycles involving dehyd...... a rate-determining phosphine dissociation for the decarbonylation of aldehydes....

  10. Remotely Controlled Iridium-Catalyzed Asymmetric Hydrogenation of Terminal 1,1-Diaryl Alkenes

    NARCIS (Netherlands)

    Besset, T.; Gramage-Doria, R.; Reek, J.N.H.


    The presence of a remote directing group on terminal 1,1-diaryl and 1,1-dialkyl alkenes led to high and unprecedented enantioselectivity in iridium-catalyzed asymmetric hydrogenation (see scheme). This strategy offers efficient synthetic pathways towards valuable enantiomerically enriched 1,1-diaryl

  11. Potential contributions to space geodesy from the IridiumNEXT constellation (United States)

    Gunter, B. C.; Encarnação, J.; Ditmar, P.; Klees, R.


    The IridiumNEXT constellation will soon replace the existing Iridium satellite telecommunication network, with initial launches set to start in 2015. In addition to the primary task of providing global telecommunication services, each IridiumNEXT satellite will also carry a hosted payload that will provide both private and public institutions the opportunity to place an instrument suite on one or all of constellation's satellites. This creates the possibility to gather continuous, global observations of Earth over the entire 15 year projected mission lifetime. Access to such a platform creates the potential to investigate many of Earth's highly dynamic processes at a spatiotemporal resolution that is simply not possible from single-satellite missions. Space geodesy is one the numerous fields that would benefit from such a mission. Precise orbits of the IridiumNEXT satellites derived through an on-board GNSS receiver (plus accelerometers and star cameras) have the potential to observe the large-scale, high-frequency variations in Earth's gravity field at time scales as short as one day. Additional positioning data from ground-based laser ranging stations would help improve the orbit determination, in addition to providing the necessary link to improve estimates of geocenter motion and reference frames. In this presentation, we will analyze the expected geodetic science returns from such a mission and will discuss the instrumental requirements needed to achieve these objectives.

  12. A pH Sensor Based on a Stainless Steel Electrode Electrodeposited with Iridium Oxide (United States)

    Martinez, C. C. M.; Madrid, R. E.; Felice, C. J.


    A simple procedure to make an iridium oxide (IrO[subscript 2]) electrodeposited pH sensor, that can be used in a chemical, biomedical, or materials laboratory, is presented here. Some exercises, based on this sensor, that can be used to teach important concepts in the field of biomedical, biochemical, tissue, or materials engineering, are also…

  13. Hyperbranched red light-emitting phosphorescent polymers based on iridium complex as the core

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Ting; Yu, Lei; Yang, Yong; Li, Yanhu; Tao, Yun [Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640 (China); Hou, Qiong [School of Chemistry & Environment, South China Normal University, Guangzhou 510006 (China); Ying, Lei, E-mail: [Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640 (China); Yang, Wei; Wu, Hongbin; Cao, Yong [Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640 (China)


    A series of hyperbranched π-conjugated light-emitting polymers containing an iridium complex as the branched core unit and polyfluorene or poly(fluorene-alt-carbazole) as the branched segments were synthesized via a palladium catalyzed Suzuki polymerization. Apparent Förster energy transfer in the photoluminescent spectra as thin films was observed, while no discernible characteristic absorbance and photoluminescence of the iridium complex can be realized in dilute solutions. Copolymers based on poly(fluorene-alt-carbazole) as the branched segments demonstrated enhanced highest occupied molecular orbital energy levels relative to those based on polyfluorene. The electroluminescent spectra of these copolymers exclusively showed the characteristic emission of the iridium complex, with corresponding CIE coordinates of (0.67±0.01, 0.31). All devices exhibited relatively slow roll-off of efficiency, and the best device performance with the maximum luminous efficiency of 5.33 cd A{sup −1} was attained by using PFCzTiqIr3 as the emissive layer. These results indicated that the hyperbranched conjugated architectures can be a promising molecular design strategy for efficient electrophosphorescent light-emitting polymers. - Highlights: • Hyperbranched red light-emitting polymers are synthesized. • Red light-emitting iridium complex is used as the branched core unit. • Hyperbranched polymers based on PFCz exhibit higher luminescence. • The highest luminous efficiency of 5.33 cd A{sup −1} is attained.

  14. Advances in Photocatalysis: A Microreview of Visible Light Mediated Ruthenium and Iridium Catalyzed Organic Transformations. (United States)

    Day, Jon I; Teegardin, Kip; Weaver, Jimmie; Chan, John


    Photocatalytic organic transformations utilizing ruthenium and iridium complexes have garnered significant attention due to the access they provide to new synthetic spaces through new reaction mechanisms. A survey of the photophysical data and the diversity of transformations that may be accomplished utilizing commercially available photocatalysts is contained herein.

  15. Synthesis and Photoluminescence of a New Red Phosphorescent Iridium(III) Quinoxaline Complex

    Institute of Scientific and Technical Information of China (English)

    Guo Lin ZHANG; Ze Hua LIU; Hai Qing GUO


    A new cyclometalated iridium(III) complex with the formula [Ir(DPQ)2(acac)] (DPQ= 2,3-diphenylquinoxaline; acac=acetylacetone) was prepared. The structure of the complex was confirmed by Elemental Analysis (EA), 1H NMR, and mass spectroscopy (MS). The UV-vis absorption and photoluminescent properties of the complex were investigated.

  16. Green and blue electrochemically generated chemiluminescence from click chemistry—customizable iridium complexes

    NARCIS (Netherlands)

    Zanarini, S.; Felici, M.; Valenti, G.; Marcaccio, M.; Prodi, L.; Bonacchi, S.; Contreras-Carballada, P.; Williams, R.M.; Feiters, M.C.; Nolte, R.J.M.; De Cola, L.; Paolucci, F.


    Cationic cyclometalated iridium complexes containing two anionic phenylpyridine (ppy) ligands and the neutral bidentate triazole-pyridine ligand, 2-(1-substituted-1H-1,2,3-triazol-4-yl)pyridine (pytl), were investigated. The complexes display a rich and reversible electrochemical behavior, upon inve

  17. A pH Sensor Based on a Stainless Steel Electrode Electrodeposited with Iridium Oxide (United States)

    Martinez, C. C. M.; Madrid, R. E.; Felice, C. J.


    A simple procedure to make an iridium oxide (IrO[subscript 2]) electrodeposited pH sensor, that can be used in a chemical, biomedical, or materials laboratory, is presented here. Some exercises, based on this sensor, that can be used to teach important concepts in the field of biomedical, biochemical, tissue, or materials engineering, are also…

  18. Synthesis and Luminescence Properties of Iridium(III Azide- and Triazole-Bisterpyridine Complexes

    Directory of Open Access Journals (Sweden)

    Timothy W. Schmidt


    Full Text Available We describe here the synthesis of azide-functionalised iridium(III bisterpyridines using the “chemistry on the complex” strategy. The resulting azide-complexes are then used in the copper(I-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition “click chemistry” reaction to from the corresponding triazole-functionalised iridium(III bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III bisterpyridines, but this effect can be reversed by the addition of copper(II sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III bisterpyridines can be functionalized for use in “click chemistry” facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

  19. Nanoporous sputtered platinum-iridium-thinfilms for medical and energy applications; Nanoporoese gesputterte Platin-Iridium-Schichten fuer Anwendungen in der Medizin- und Energietechnik

    Energy Technology Data Exchange (ETDEWEB)

    Ganske, Gerald


    Sputtering makes it possible to create thinfilms of only a few atom layers and to customize them for special applications by adjusting the deposition parameters. In this work interface-layers are deposited and characterized in biological systems as stimulation electrodes for neural cells and as catalysts in hydrogen fuel cells. First of all, highly porous platinum films were created by sputtering at a pressure of 9 Pa and low power of less than 100 W. These parameters are an ideal compromise between deposition rate, porosity and disordered crystal structure of the layers. Investigations on co-sputtered platinum-iridium-films (PtIr) showed that these films form homogeneous structures and no distinction between the separate layers is possible. It was demonstrated that these films obtain the crystal structure of Pt as well as the finer cauliflower-like structure of iridium, if the atoms reach the substrate surface only with their thermal energy. Furthermore, it was shown that the film composition reflects the sputtering power of the separate targets in a linear way. The structure of the films can be predicted by means of monte-carlo-simulation, which was verified by SEM-pictures. The ratio of the sputtering power can be used to control the amount of interface elements which was confirmed by electrochemical tests. Electrode materials for the stimulation of neural cells need a large electrochemically active surface that allows for an interface between electron and ion conductivity. Test on platinum, iridium and PtIr have shown that the films sputtered at the lowest impact energy do have the largest active surface as well as the largest charge delivery capacity (CDC). Iridium films show the highest CDC (48 mC/cm{sup 2}), followed by platinum-iridium (2 mC/cm{sup 2}, 100 W power at both targets) and pure platinum (16 mC/cm{sup 2}). This can be explained by the large surface area of iridium and its electrochemical activation process. Although PtIr layers also show an

  20. Testing of electroformed deposited iridium/powder metallurgy rhenium rockets (United States)

    Reed, Brian D.; Dickerson, Robert


    High-temperature, oxidation-resistant chamber materials offer the thermal margin for high performance and extended lifetimes for radiation-cooled rockets. Rhenium (Re) coated with iridium (Ir) allow hours of operation at 2200 C on Earth-storable propellants. One process for manufacturing Ir/Re rocket chambers is the fabrication of Re substrates by powder metallurgy (PM) and the application of Ir coatings by using electroformed deposition (ED). ED Ir coatings, however, have been found to be porous and poorly adherent. The integrity of ED Ir coatings could be improved by densification after the electroforming process. This report summarizes the testing of two 22-N, ED Ir/PM Re rocket chambers that were subjected to post-deposition treatments in an effort to densify the Ir coating. One chamber was vacuum annealed, while the other chamber was subjected to hot isostatic pressure (HIP). The chambers were tested on gaseous oxygen/gaseous hydrogen propellants, at mixture ratios that simulated the oxidizing environments of Earth-storable propellants. ne annealed ED Ir/PM Re chamber was tested for a total of 24 firings and 4.58 hr at a mixture ratio of 4.2. After only 9 firings, the annealed ED Ir coating began to blister and spall upstream of the throat. The blistering and spalling were similar to what had been experienced with unannealed, as-deposited ED Ir coatings. The HIP ED Ir/PM Re chamber was tested for a total of 91 firings and 11.45 hr at mixture ratios of 3.2 and 4.2. The HIP ED Ir coating remained adherent to the Re substrate throughout testing; there were no visible signs of coating degradation. Metallography revealed, however, thinning of the HIP Ir coating and occasional pores in the Re layer upstream of the throat. Pinholes in the Ir coating may have provided a path for oxidation of the Re substrate at these locations. The HIP ED Ir coating proved to be more effective than vacuum annealed and as-deposited ED Ir. Further densification is still required to

  1. Asymmetric hydrogenation of quinazolinium salts catalysed by halide-bridged dinuclear iridium complexes bearing chiral diphosphine ligands. (United States)

    Kita, Yusuke; Higashida, Kosuke; Yamaji, Kenta; Iimuro, Atsuhiro; Mashima, Kazushi


    Asymmetric hydrogenation of quinazolinium salts was catalysed by halogen-bridged dinuclear iridium complexes bearing chiral diphosphine ligands, yielding tetrahydroquinazoline and 3,4-dihydroquinazoline with high enantioselectivity. A derivative of chiral dihydroquinazoline was used as a chiral NHC ligand.

  2. Reducing HAuCl4 by the C60 dianion: C60-directed self-assembly of gold nanoparticles into novel fullerene bound gold nanoassemblies (United States)

    Liu, Wei; Gao, Xiang


    The C60 dianion is used to reduce tetrachloroauric acid (HAuCl4) for the first time; three-dimensional C60 bound gold (Au-C60) nanoclusters are obtained from C60-directed self-assembly of gold nanoparticles due to the strong affinities of Au-C60 and C60-C60. The process was monitored in situ by UV-vis-NIR spectroscopy. The resulting Au-C60 nanoclusters were characterized using transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy-dispersive spectroscopy (EDS), x-ray powder diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and FT-IR and Raman spectroscopies. TEM demonstrates the formation of 3D nanonetwork aggregates, which are composed of discrete gold nanocores covered with a C60 monolayer. The SAED and XRD patterns indicate that the gold nanocores inside the capped C60 molecules belong to the face-centred cubic crystal structure, while the C60 molecules are amorphous. The EDS and XPS measurements validate that the Au-C60 nanoclusters contain only Au and C elements and Au3+ is reduced to Au0. FT-IR spectroscopy shows the chemiadsorption of C60 to the gold nanocores, while Raman spectroscopy demonstrates the electron transfer from the gold nanocores to the chemiadsorbed C60 molecules. Au-C60 nanoclusters embedded in tetraoctyl-n-ammonium bromide (TOAB) on glassy carbon electrodes (GCEs) have been fabricated and have shown stable and well-defined electrochemical responses in aqueous solution.

  3. Solvent evaporation versus proton transfer in nucleobase-Pt(CN)(4,6)²⁻ dianion clusters: a collisional excitation and electronic laser photodissociation spectroscopy study. (United States)

    Sen, Ananya; Luxford, Thomas F M; Yoshikawa, Naruo; Dessent, Caroline E H


    Isolated molecular clusters of adenine, cytosine, thymine and uracil with Pt(CN)6(2-) and Pt(CN)4(2-) were studied for the first time to characterize the binding and reactivity of isolated transition metal complex ions with nucleobases. These clusters represent model systems for understanding metal complex-DNA adducts, as a function of individual nucleobases. Collisional excitation revealed that the clusters decay on the ground electronic surface by either solvent evaporation (i.e. loss of a nucleobase unit from the cluster) or via proton transfer from the nucleobase to the dianion. The Pt(CN)6(2-)-nucleobase clusters decay only by solvent evaporation, while the Pt(CN)4(2-) clusters fragment by both pathways. The enhanced proton-transfer reactivity of Pt(CN)4(2-) is attributed to the higher charge-density of the ligands in this transition metal anion. % fragmentation curves of the clusters reveal that the adenine clusters display distinctively higher fragmentation onsets, which are traced to the propensity of adenine to form the shortest intercluster H-bond. We also present laser electronic photodissociation measurements for the Pt(CN)6(2-)·Ur, Pt(CN)4(2-)·Ur and Pt(CN)4(2-)·Ur2 clusters to illustrate the potential of exploring metal complex DNA photophysics as a function of nucleobase within well-defined gaseous clusters. The spectra reported herein represent the first such measurements. We find that the electronic excited states decay with production of the same fragments (associated with solvent evaporation and proton transfer) observed upon collisional excitation of the electronic ground state, indicating ultrafast deactivation of the excited-state uracil-localized chromophore followed by vibrational predissociation.

  4. Time-resolved photoelectron spectroscopy of a dinuclear Pt(II) complex: Tunneling autodetachment from both singlet and triplet excited states of a molecular dianion

    Energy Technology Data Exchange (ETDEWEB)

    Winghart, Marc-Oliver, E-mail:; Unterreiner, Andreas-Neil [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); Yang, Ji-Ping [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); School of Sciences, Hefei University of Technology, Hefei 230009 (China); Vonderach, Matthias [Centre for Proteome Research, Institute of Integrative Biology, University of Liverpool, Liverpool L69 7ZB (United Kingdom); Huang, Dao-Ling; Wang, Lai-Sheng [Department of Chemistry, Brown University, Providence, Rhode Island 02912 (United States); Kruppa, Sebastian; Riehn, Christoph [Fachbereich Chemie und Landesforschungszentrum OPTIMAS, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Kappes, Manfred M., E-mail: [Institute of Physical Chemistry, Karlsruhe Institute of Technology, P.O. Box 6980, 76049 Karlsruhe (Germany); Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe (Germany)


    Time-resolved pump-probe photoelectron spectroscopy has been used to study the relaxation dynamics of gaseous [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} after population of its first singlet excited state by 388 nm femtosecond laser irradiation. In contrast to the fluorescence and phosphorescence observed in condensed phase, a significant fraction of the photoexcited isolated dianions decays by electron loss to form the corresponding monoanions. Our transient photoelectron data reveal an ultrafast decay of the initially excited singlet {sup 1}A{sub 2u} state and concomitant rise in population of the triplet {sup 3}A{sub 2u} state, via sub-picosecond intersystem crossing (ISC). We find that both of the electronically excited states are metastably bound behind a repulsive Coulomb barrier and can decay via delayed autodetachment to yield electrons with characteristic kinetic energies. While excited state tunneling detachment (ESETD) from the singlet {sup 1}A{sub 2u} state takes only a few picoseconds, ESETD from the triplet {sup 3}A{sub 2u} state is much slower and proceeds on a time scale of hundreds of nanoseconds. The ISC rate in the gas phase is significantly higher than in solution, which can be rationalized in terms of changes to the energy dissipation mechanism in the absence of solvent molecules. [Pt{sub 2}(μ-P{sub 2}O{sub 5}H{sub 2}){sub 4} + 2H]{sup 2−} is the first example of a photoexcited multianion for which ESETD has been observed following ISC.

  5. A novel dianionic amino acid ionic liquid-coated PEG 4000 modified Fe3O4 nanocomposite for the magnetic solid-phase extraction of trypsin. (United States)

    Yang, Qin; Wang, Yuzhi; Zhang, Hongmei; Xu, Kaijia; Wei, Xiaoxiao; Xu, Panli; Zhou, Yigang


    A novel magnetic extractant, PEG 4000 modified Fe3O4nanomaterial that coated with dianionic amino acid ionic liquid (Fe3O4@PEG@DAAAIL), was successfully synthesized and characterized. X-ray diffraction (XRD), transmission electron microscope (TEM), vibrating sample magnetometer (VSM), fourier transform infrared spectrometry (FT-IR), thermal gravimetric analysis (TGA) and zeta potentials were used to confirm that the novel nanocomposite was successfully synthesized. Subsequently, the prepared Fe3O4@PEG@DAAAIL nanocomposite was used as the extractant for trypsin coupled with magnetic solid-phase extraction (MSPE). The concentrations of trypsin in the supernatant were detected by UV-vis spectrophotometer at 278nm. The extraction ability turned out to be better than the other four kinds of extractants prepared in this work. Furthermore, the influence of a series of factors, such as extraction time and temperature, initial trypsin concentration, the value of pH and ionic strength, was systematically investigated. Under the optimal extraction condition, the extraction capacity for trypsin could reach up to 718.73mg/g, absolutely higher than that of other adsorbents reported. This satisfactory extraction capacity could be maintained unchangeable after at least eight days, and kept over 90% of initial extraction capacity after eight recycles. What's more, the activity of trypsin after extraction retained 92.29% of initial activity, verifying the biocompatibility of the prepared extractant. Finally, the developed Fe3O4@PEG@DAAAIL-MSPE method was successfully applied to the real sample analysis with satisfactory results. All of above proves the potential value of Fe3O4@PEG@DAAAIL-MSPE in the analysis of biomass. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Highly active iridium/iridium-tin/tin oxide heterogeneous nanoparticles as alternative electrocatalysts for the ethanol oxidation reaction. (United States)

    Du, Wenxin; Wang, Qi; Saxner, David; Deskins, N Aaron; Su, Dong; Krzanowski, James E; Frenkel, Anatoly I; Teng, Xiaowei


    Ethanol is a promising fuel for low-temperature direct fuel cell reactions due to its low toxicity, ease of storage and transportation, high-energy density, and availability from biomass. However, the implementation of ethanol fuel cell technology has been hindered by the lack of low-cost, highly active anode catalysts. In this paper, we have studied Iridium (Ir)-based binary catalysts as low-cost alternative electrocatalysts replacing platinum (Pt)-based catalysts for the direct ethanol fuel cell (DEFC) reaction. We report the synthesis of carbon supported Ir(71)Sn(29) catalysts with an average diameter of 2.7 ± 0.6 nm through a "surfactant-free" wet chemistry approach. The complementary characterization techniques, including aberration-corrected scanning transmission electron microscopy equipped with electron energy loss spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy, are used to identify the "real" heterogeneous structure of Ir(71)Sn(29)/C particles as Ir/Ir-Sn/SnO(2), which consists of an Ir-rich core and an Ir-Sn alloy shell with SnO(2) present on the surface. The Ir(71)Sn(29)/C heterogeneous catalyst exhibited high electrochemical activity toward the ethanol oxidation reaction compared to the commercial Pt/C (ETEK), PtRu/C (Johnson Matthey) as well as PtSn/C catalysts. Electrochemical measurements and density functional theory calculations demonstrate that the superior electro-activity is directly related to the high degree of Ir-Sn alloy formation as well as the existence of nonalloyed SnO(2) on surface. Our cross-disciplinary work, from novel "surfactant-free" synthesis of Ir-Sn catalysts, theoretical simulations, and catalytic measurements to the characterizations of "real" heterogeneous nanostructures, will not only highlight the intriguing structure-property correlations in nanosized catalysts but also have a transformative impact on the commercialization of DEFC technology by replacing Pt with low

  7. An Analysis of the FY-1C, Iridium 33, and Cosmos 2251 Fragments (United States)

    Liou, J.-C.


    The beginning of the year 2013 marks the sixth anniversary of the destruction of the Fengyun-1C (FY-1C) weather satellite as the result of an anti-satellite test conducted by China in January 2007 and the fourth anniversary of the accidental collision between Cosmos 2251 and the operational Iridium 33 in February 2009. These two events represent the worst satellite breakups in history. A total of 5579 fragments have been cataloged by the U.S. Space Surveillance Network (SSN), and almost 5000 of them were still in orbit in January 2013. In addition to these cataloged objects, hundreds of thousands (or more) of fragments down to the millimeter size regime were also generated during the breakups. These fragments are too small to be tracked by the SSN, but are large enough to be a safety concern for human space activities and robotic missions in low Earth orbit (LEO, the region below 2000 km altitude). Like their cataloged siblings, many of them remain in orbit today. These two breakup events dramatically changed the landscape of the orbital debris environment in LEO. The spatial density of the cataloged population in January 2013 is shown as the top blue curve. The combined FY-1C, Iridium 33, and Cosmos 2251 fragments (black curve) account for about 50 percent of the cataloged population below an altitude of 1000 km. They are also responsible for the concentrations at 770 km and 850 km, altitudes at which the collisions occurred. The effects of the FY-1C, Iridium 33, and Cosmos 2251 fragments will continue to be felt for decades to come. For example, approximately half of the generated FY-1C fragments will remain in orbit 20 years from now. In general, the Iridium 33 and Cosmos 2251 fragments will decay faster than the FY-1C fragments because of their lower altitudes. Of the Iridium 33 and Cosmos 2251 fragments, the former have much shorter orbital lifetimes than the latter, because lightweight composite materials were heavily used in the construction of the Iridium

  8. Iridium and ruthenium catalyzed syntheses, hydroborations, and metathesis reactions of alkenyl-decaboranes. (United States)

    Chatterjee, Shahana; Carroll, Patrick J; Sneddon, Larry G


    The selective syntheses of new classes of 6,9-dialkenyl- and 6-alkenyl-decaboranes and 6-alkyl-9-alkenyl-decaboranes have been achieved via iridium and ruthenium catalyzed decaborane and 6-alkyl-decaborane alkyne-hydroborations. Reactions employing [Cp*IrCl2]2 and [RuCl2(p-cymene)]2 precatalysts gave β-E-alkenyl-decaboranes, while the corresponding reactions with [RuI2(p-cymene)]2 gave the α-alkenyl-decaborane isomers, with the differences in product selectivity suggesting quite different mechanistic steps for the catalysts. The alkenyl-decaboranes were easily converted to other useful derivatives, including coupled-cage and functionally substituted compounds, via iridium-catalyzed hydroborations and ruthenium-catalyzed homo and cross olefin-metathesis reactions.

  9. First Applications of DoD Iridium RUDICS in the NSF Polar Programs (United States)

    Valentic, T.; Stehle, R.


    We will present the first deployment and application of the new Iridium RUDICS service to remote instrumentation projects within the National Science Foundation's polar programs. The rise of automated observing networks has increased the demand for real-time connectivity to remote instruments, not only for immediate access to data, but to also interrogate health and status. Communicating with field sites in the polar regions is complicated by the remoteness from existing infrastructure, low temperatures and limited connection options. Sites located above 78° latitude are not able to see geostationary satellites, leaving the Iridium constellation as the only one that provide a direct connection. Some others, such as Orbcomm, only provide a store-and-forward service. Iridium is often used as a dial up modem to establish a PPP connection to the Internet with data files transferred via FTP. On low-bandwidth, high-latency networks like Iridium (2400bps with ping times of seconds), this approach is time consuming and inefficient. The dial up time alone takes upwards of a minute, and standard TCP/IP and FTP protocols are hampered by the long latencies. Minimizing transmission time is important for reducing battery usage and connection costs. The new Iridium RUDICS service can be used for more efficient transfers. RUDICS is an acronym for "Router-based Unstructured Digital Inter-working Connectivity Solution" and provides a direct connection between an instrument in the field and a server on the Internet. After dialing into the Iridium gateway, a socket connection is opened to a registered port on a user's server. Bytes sent to or from the modem appear at the server's socket. The connection time is reduced to about 10 seconds because the modem training and PPP negotiation stages are eliminated. The remote device does not need to have a full TCP/IP stack, allowing smaller instruments such as data loggers to directly handle the data transmission. Alternative protocols can

  10. Grain Growth and Precipitation Behavior of Iridium Alloy DOP-26 During Long Term Aging

    Energy Technology Data Exchange (ETDEWEB)

    Pierce, Dean T. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Muralidharan, Govindarajan [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Fox, Ethan E. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Cox, Victoria A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Geer, Tom [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)


    The influence of long term aging on grain growth and precipitate sizes and spatial distribution in iridium alloy DOP-26 was studied. Samples of DOP-26 were fabricated using the new process, recrystallized for 1 hour (h) at 1375 C, then aged at either 1300, 1400, or 1500 C for times ranging from 50 to 10,000 h. Grain size measurements (vertical and horizontal mean linear intercept and horizontal and vertical projection) and analyses of iridium-thorium precipitates (size and spacing) were made on the longitudinal, transverse, and rolling surfaces of the as-recrystallized and aged specimens from which the two-dimensional spatial distribution and mean sizes of the precipitates were obtained. The results obtained from this study are intended to provide input to grain growth models.

  11. Origins of Enantioselectivity during Allylic Substitution Reactions Catalyzed by Metallacyclic Iridium Complexes


    Madrahimov, Sherzod T.; Hartwig, John F.


    In depth mechanistic studies of iridium catalyzed regioselective and enantioselective allylic substitution reactions are presented. A series of cyclometallated allyliridium complexes that are kinetically and chemically competent to be intermediates in the allylic substitution reactions was prepared and characterized by 1D and 2D NMR spectroscopies and solid state structural analysis. The rates of epimerization of the less thermodynamically stable diastereomeric allyliridium complexes to the t...

  12. The laser welding of iridium-platinum tips to spark plug electrodes (United States)

    Antoszewski, Bogdan; Tofil, Szymon


    The paper presents selected results of model and technological experiments of welding iridium-platinum tips to spark plug electrodes. Variants of welding technology included different ways of preparing materials and the use of different Nd: YAG lasers (Rofin BLS 720 and Rofin Integral). The results of technological tests were verified by the metallographic evaluation of joints. Performance tests when powered by biogas were conducted for selected variants of welding.

  13. Biocompatibility and durability of Teflon-coated platinum-iridium wires implanted in the vitreous cavity. (United States)

    Nishida, Kentaro; Sakaguchi, Hirokazu; Xie, Ping; Terasawa, Yasuo; Ozawa, Motoki; Kamei, Motohiro; Nishida, Kohji


    Teflon-coated platinum-iridium wires are placed in the vitreous as electrodes in artificial vision systems. The purpose of this study was to determine whether these wires have toxicity in the vitreous cavity, and to examine the durability of their coating when grasped by forceps. Rabbits were implanted with platinum-iridium wires that were 50 μm in diameter and coated with Teflon to a total diameter of 68 or 100 μm. To examine the biocompatibility, electroretinograms (ERGs) and fluorescein angiography (FA) were performed before and 1 week, 1, 3, and 6 months after the implantation of the electrode. After 6 months, the eyes were histologically examined with light microscopy. To check the durability, the surface of a coated wire was examined with scanning electron microscopy after grasping with different types of forceps. At all times after the implantation the amplitudes and implicit times of the ERGs recorded were not significantly different from those recorded before the implantation (P > 0.05). FA showed no notable change during the follow-up periods. Histological studies showed that the retinas were intact after 6 months of implantation. There was no damage to the Teflon-coated wire after grasping the wire with forceps with silicon-coated tips, while surface damage of the Teflon that did not extend to the platinum-iridium wire was found when grasped by vitreoretinal forceps. We conclude that Teflon-coated platinum-iridium wire is highly biocompatible in the vitreous for at least 6 months. Wires should be handled with vitreoretinal forceps with silicone-coated tips in order to avoid causing damage during wire manipulation.

  14. Novel Iridium (III) complexes for photocatalytic H2 generation from H2O using sunlight


    Soman, Suraj


    The design and synthesis of economically viable homogeneous and heterogeneous transition metal complexes for photocatalytic hydrogen generation using visible light irradiation and as OLED’s are under intense investigation. Transition metal complexes are drawing great interest as they offer highly efficient room temperature phosphorescence. In particular iridium (III) complexes are considered to be the most promising since they exhibit: (1) good photo and thermal stabilities, (2) high phosphor...

  15. Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with secondary amine nucleophiles

    Directory of Open Access Journals (Sweden)

    Dingqiao Yang


    Full Text Available Iridium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes with various aliphatic and aromatic secondary amines are reported for the first time. The reaction gave the corresponding trans-1,2-dihydronaphthalenol derivatives in good yields with moderate enantioselectivities in the presence of 2.5 mol % [Ir(CODCl]2 and 5 mol % bisphosphine ligand (S-p-Tol-BINAP. The trans-configuration of 3f was confirmed by X-ray crystallography.

  16. Iridium thin films deposited via pulsed laser deposition for future applications as transition-edge sensors

    Energy Technology Data Exchange (ETDEWEB)

    Galeazzi, M. E-mail:; Chen, C.; Cohn, J.L.; Gundersen, J.O


    The University of Miami has recently started developing and studying high-resolution microcalorimeters operating near 100 mK for X-ray and particle physics and astrophysics. These detectors will be based on Transition Edge Sensors technology fabricated using iridium thin films deposited via the Pulsed Laser Deposition technique. We report here the preliminary result of the room temperature characterization of the Ir thin films, and an overview of future plans to use the films as transition edge sensors.

  17. Neutron activation determination of iridium, gold, platinum, and silver in geologic samples (United States)

    Millard, H.T.


    Low-level methods for the determination of iridium and other noble metals have become increasingly important in recent years due to interest in locating abundance anomalies associated with the Cretaceous and Tertiary (K-T) boundary. Typical iridium anomalies are in the range of 1 to 100 ??g/kg (ppb). Thus methods with detection limits near 0.1 ??g/kg should be adequate to detect K-T boundary anomalies. Radiochemical neutron activation analysis methods continue to be required although instrumental neutron activation analysis techniques employing elaborate gamma-counters are under development. In the procedure developed in this study samples irradiated in the epithermal neutron facility of the U. S. Geological Survey TRIGA Reactor (Denver, Colorado) are treated with a mini-fire assay technique. The iridium, gold, and silver are collected in a 1-gram metallic lead button. Primary contaminants at this stage are arsenic and antimony. These can be removed by heating the button with a mixture of sodium perioxide and sodium hydroxide. The resulting 0.2-gram lead bead is counted in a Compton suppression spectrometer. Carrier yields are determined by reirradiation of the lead beads. This procedure has been applied to the U.S.G.S. Standard Rock PCC-1 and samples from K-T boundary sites in the Western Interior of North America. ?? 1987 Akade??miai Kiado??.

  18. Ultrasonic detection of laminar-type defects in iridium alloy blanks

    Energy Technology Data Exchange (ETDEWEB)

    Cook, K.V.; Cunningham, R.A. Jr.; Simpson, W.A. Jr.; McClung, R.W.


    Encapsulated isotopic heat sources for use in generating electrical power for space applications require flight-quality hardware material. Iridium is the chosen material for such applications, and Oak Ridge National Laboratory has been the prime supplier of iridium alloy forming blanks 52 mm in diameter by 0.66 mm thick (1.0 by 0.026 in.). Prior to the work reported here, these blanks were ultrasonically examined by using 0.9-mm-diam (0.035-in.) simulated flaw standards. However, as a result of this effort, the sensitivity of our ultrasonic pulse-echo test system has been increased. The improved ultrasonic test system permits blank inspection at the 0.5-mm-diam (0.020-in.) simulated flaw detection level. This test system was successfully demonstrated on the initial blanks provided via an improved processing route (consumable arc-melting, extruding, and rolling). The equipment modification and/or selection and the specific focused search unit immersion technique developed to provide this capability are described. The improved flaw detection capability also provides data maps of a common type of defect in iridium (delaminations).

  19. The kinetics and mechanism of the organo-iridium catalysed racemisation of amines. (United States)

    Stirling, Matthew J; Mwansa, Joseph M; Sweeney, Gemma; Blacker, A John; Page, Michael I


    The dimeric iodo-iridium complex [IrCp*I2]2 (Cp* = pentamethylcyclopentadiene) is an efficient catalyst for the racemisation of secondary and tertiary amines at ambient and higher temperatures with a low catalyst loading. The racemisation occurs with pseudo-first-order kinetics and the corresponding four rate constants were obtained by monitoring the time dependence of the concentrations of the (R) and (S) enantiomers starting with either pure (R) or (S) and show a first-order dependence on catalyst concentration. Low temperature (1)H NMR data is consistent with the formation of a 1 : 1 complex with the amine coordinated to the iridium and with both iodide anions still bound to the metal-ion, but at the higher temperatures used for kinetic studies binding is weak and so no saturation zero-order kinetics are observed. A cross-over experiment with isotopically labelled amines demonstrates the intermediate formation of an imine which can dissociate from the iridium complex. Replacing the iodides in the catalyst by other ligands or having an amide substituent in Cp* results in a much less effective catalysts for the racemisation of amines. The rate constants for a deuterated amine yield a significant primary kinetic isotope effect kH/kD = 3.24 indicating that hydride transfer is involved in the rate-limiting step.

  20. Half-sandwich iridium complexes for homogeneous water-oxidation catalysis. (United States)

    Blakemore, James D; Schley, Nathan D; Balcells, David; Hull, Jonathan F; Olack, Gerard W; Incarvito, Christopher D; Eisenstein, Odile; Brudvig, Gary W; Crabtree, Robert H


    Iridium half-sandwich complexes of the types Cp*Ir(N-C)X, [Cp*Ir(N-N)X]X, and [CpIr(N-N)X]X are catalyst precursors for the homogeneous oxidation of water to dioxygen. Kinetic studies with cerium(IV) ammonium nitrate as primary oxidant show that oxygen evolution is rapid and continues over many hours. In addition, [Cp*Ir(H(2)O)(3)]SO(4) and [(Cp*Ir)(2)(μ-OH)(3)]OH can show even higher turnover frequencies (up to 20 min(-1) at pH 0.89). Aqueous electrochemical studies on the cationic complexes having chelate ligands show catalytic oxidation at pH > 7; conversely, at low pH, there are no oxidation waves up to 1.5 V vs NHE for the complexes. H(2)(18)O isotope incorporation studies demonstrate that water is the source of oxygen atoms during cerium(IV)-driven catalysis. DFT calculations and kinetic experiments, including kinetic-isotope-effect studies, suggest a mechanism for homogeneous iridium-catalyzed water oxidation and contribute to the determination of the rate-determining step. The kinetic experiments also help distinguish the active homogeneous catalyst from heterogeneous nanoparticulate iridium dioxide.

  1. One- and two-photon absorption of fluorescein dianion in water: a study using S-QM/MM methodology and ZINDO method. (United States)

    Silva, D L; Barreto, R C; Lacerda, E G; Coutinho, K; Canuto, S


    One- and two-photon absorption (1PA and 2PA) of fluorescein dianion (FSD) in water were studied using a combined and sequential Quantum Mechanics/Molecular Dynamics methodology. Different sets of 250 statistically relevant (uncorrelated) configurations composed by the solute and several solvent molecules were sampled from the classical simulation. On these configurations, the electronic properties were calculated a posteriori using the Zerner's intermediate neglect of differential overlap (ZINDO) method. The linear and nonlinear absorption of FSD in water were calculated using discrete and explicit solvent models. In the largest case, the relevant configurations are composed by FSD and 47 explicit water molecules embedded in the electrostatic field of all remaining water molecules. Both INDO/CIS and INDO/CISD calculations were performed to study the absorption processes of FSD and the Sum-Over-States (SOS) model was used to describe the 2PA process. A semi-classical method for spectrum simulations was employed to simulate the 1PA and 2PA cross-section spectra of FSD in water. For comparison purposes, in the case of the 2PA process two approaches, the "full expression" and "resonant expression" methods, were employed to simulate the nonlinear spectrum. The last method assumes resonant conditions and on the computation point of view it represents an interesting option to study the 2PA process. The INDO/CI calculations give a satisfactory description of the 1PA spectrum of FSD and properly describe the unusual blue-shift of its first π→π(*) transition in water. In the case of 2PA, the introduction of doubly excited configuration interactions (INDO/CISD) has proven to be essential for an appropriate description of the process at the higher energy spectral region. It was observed that the solvent effects do not drastically change the cross-sections of both processes. The simulated 2PA cross-section spectrum provided by the "full expression" method presents a better

  2. Grain Growth Behavior, Tensile Impact Ductility, and Weldability of Cerium-Doped Iridium Alloys

    Energy Technology Data Exchange (ETDEWEB)

    McKamey, C.G.


    An iridium alloy doped with small amounts of cerium and thorium is being developed as a potential replacement for the iridium-based DOP-26 alloy (doped with thorium only) that is currently used by the National Aeronautics and Space Administration (NASA) for cladding and post-impact containment of the radioactive fuel in radioisotope thermoelectric generator (RTG) heat sources which provide electric power for interplanetary spacecraft. This report summarizes results of studies conducted to date under the Iridium Alloy Characterization and Development subtask of the Radioisotope Power System Materials Production and Technology Program to characterize the properties of the iridium-based alloy (designated as DOP-40) containing both cerium and thorium. Included within this report are data on grain growth of sheet material in vacuum and low-pressure oxygen environments, grain growth in vacuum of the clad vent set cup material, weldability, and the effect of grain size and test temperature on tensile properties. Where applicable, data for the DOP-26 alloy are included for comparison. Both grain size and grain-boundary cohesion affect the ductility of iridium alloys. In this study it was found that cerium and thorium, when added together, refine grain size more effectively than when thorium is added by itself (especially at high temperatures). In addition, the effect of cerium additions on grain-boundary cohesion is similar to that of thorium. Mechanical testing at both low ({approx} 10{sup -3}s{sup -1}) and high ({approx} 10{sup -3}s{sup -1}) strain rates showed that the Ce/Th-doped alloys have tensile ductilities that are as good or better than the DOP-26 alloy. The general conclusion from these studies is that cerium can be used to replace some of the radioactive thorium currently used in DOP-26 while maintaining or improving its metallurgical properties. The current DOP-26 alloy meets all requirements for cladding the radioactive fuel in the RTG heat source, but the

  3. Iridium contents in the Late Cretaceous-Early Tertiary clays in relation to the K/T boundary, North Jordan (United States)

    Abboud, Iyad Ahmed


    The mineralogy, lithology, and geochemistry of five discrete laminations across the K/T boundary of clayey shale at the Yarmouk River area, Jordan, were examined. There were no marked changes in the mineralogy of the clayey shale within the K/T boundary. This outcrop consists of more than 100 m of Maastrichtian oil shale overlying about 20 m limestone. Marly limestone included many clay laminations from organic and volcanic origins, which are considered an evidence of the K/T boundary through detected iridium anomalies. Any of these particular lamellae range from 2 mm to 5 mm in thickness. Smectite was the predominant clay mineral in smectitic shale laminations. It was located at eight meters above the K/T boundary and includes some anomalous concentrations of iridium and traces of other elements. The analysis of geochemical platinum group at the K/T boundary clays showed anomalous enrichments of iridium, compared with other carbonate rocks as a result of weathering processes of oil shale, or through concentration from weathering of basalt flows, but not pointing to an impact process. The clays in late Maastrichtian have Ir-Sc prevailed anomalies and synchronize with increasing of terrigenous and volcanogenic traced elements. Kaolin, smectite, and volkonskoite were the dominant clay minerals at the K/T boundary with high concentrations of iridium. The concentration levels of iridium in some laminations of the Yarmouk sediments ranged between 1.6 and 7.8 ppb.

  4. Synthesis and Photoluminescence of a Novel Iridium Complex (BuPhOXD)2Ir(acac) with Unit of 1, 3, 4-Oxadiazole

    Institute of Scientific and Technical Information of China (English)

    Zhong Lian WU; Mei Xiang ZHU; Yu LIU; Jian LIU; Jian Ren LI; Yu Ping YANG; Quan GAN; Wei Guo ZHU


    A novel cyclometalated iridium complex with 1, 3, 4-oxadiazole moiety was synthesized and characterized. Its UV and photoluminescent properties were studied. The strong UV absorption intensity around 462 nm attributed to spin-forbidden triplet metal-ligand charge transfer band and photoluminescence at 518 nm were observed. This indicated that achieved iridium complex could be used as an efficient electrophosphorescent material.

  5. Study of neutron deficient iridium isotopes by using laser spectroscopy; Etude des noyaux d'iridium deficients en neutrons par spectroscopie laser

    Energy Technology Data Exchange (ETDEWEB)

    Verney, D


    Resonance ionization spectroscopy was performed on neutron deficient iridium isotopes {sup 182-189}Ir, {sup 186}Ir{sup m} and stable isotopes {sup 191,193}Ir. Hyperfine spectra were recorded from the optical transition at 351,7 nm between the 5d{sup 7}6s{sup 2} {sup 4}F{sub 9/2} ground state and the 5d{sup 7}6s6p {sup 6}F{sub 11/2} excited state. Radioactive iridium isotopes were obtained from {beta}{sup +}/EC decay of radioactive mercury nuclei deposited on a graphite substrate. The radioactive mercury nuclei were produced at the ISOLDE facility at CERN through spallation reactions, by bombarding a molten lead target with the 1 GeV proton beam delivered by the PS-Booster. Magnetic dipole moments and spectroscopic quadrupole moments were extracted from the hyperfine spectra. The mean square charge radius variations, as deduced from the measured isotopic shift, show a sharp change between {sup 187}Ir and {sup 186}Ir{sup g}, accompanied by a sudden increase in deformation: from {beta}2 {approx} 0,16 to {beta}2 > 0, 2. These results were analysed in the framework of an axial rotor plus one or two quasiparticles. The wave functions of the osmium and platinum cores which are used in order to describe the iridium nuclei were calculated from the HF+BCS method with the Skyrme SIII effective interaction. The cores were constrained to take the deformation parameters extracted from the isotopic shift measurements. One shows then that this sudden deformation change corresponds also to a change in the proton state that describes the odd nuclei ground state or that participates in the coupling with the neutron in odd-odd nuclei. This state is identified with the {pi}3/2{sup +}[402] orbital for the smaller deformations nuclei and with the {pi}1/2{sup -}[541] orbital stemming from the h{sub 9/2} subshell for bigger deformations nuclei. (author)

  6. Nuclear resonance scattering study of iridates, iridium and antimony based pyrochlores

    Energy Technology Data Exchange (ETDEWEB)

    Alexeev, P.


    This thesis shows the first synchrotron-based Moessbauer spectroscopy studies on iridium containing compounds and first vibrational spectroscopy on Sb containing compounds carried out at the P01 beamline of PETRA III. In this context, two types of X-ray monochromators have been developed: a monochromator for 73 keV photons with medium energy resolution, and a high-resolution backscattering monochromator based on a sapphire crystal. The monochromator for 73 keV X-rays is the key instrument for hyperfine spectroscopy on Iridium compounds, while the sapphire backscattering monochromator is purposed to vibrational spectroscopy on any Moessbauer resonances with the transition energies in the 20-50 keV range. Additionally, the signal detection for nuclear resonance scattering experiments at the beamline was significantly improved during this work, inspired by the high energies and low lifetimes of the employed resonances. The first synchrotron-based hyperfine spectroscopy on Iridium-containing compounds was demonstrated by NRS on 73 keV resonance in {sup 193}Ir. The results can be interpreted by dynamical theory of nuclear resonance scattering. In this work, special emphasis is set onto the electronic and magnetic properties of Ir nuclei in IrO{sub 2} and in Ruddlesden-Popper (RP) phases of strontium iridates Sr{sub n+1}Ir{sub n}O{sub 3n+1} (n=0,1). These systems are well-suited for studies with X-ray scattering techniques, since the scattered signal contains vast information about the widely tunable crystallographic and electronic structure of these systems; furthermore, studies with X-rays are less limited by absorption from iridium as it is the case for neutron scattering experiments. The hyperfine parameters in IrO{sub 2}, SrIrO{sub 3} and Sr{sub 2}IrO{sub 4} have been measured via Nuclear Forward Scattering for the first time. Using the dynamical theory of NRS, the temperature and magnetic field dependence of the electric field gradient and magnetic hyperfine field

  7. Interstitial microwave-induced hyperthermia and iridium brachytherapy for the treatment of obstructing biliary carcinomas. (United States)

    Coughlin, C T; Wong, T Z; Ryan, T P; Jones, E L; Crichlow, R W; Spiegel, P K; Jeffery, R


    In a phase I clinical study, 10 patients with obstructive biliary carcinomas were treated with single-antenna interstitial microwave hyperthermia and iridium-192 brachytherapy. For each patient a standard biliary drainage catheter was implanted percutaneously through the obstructed common bile duct. This catheter accommodated a single microwave antenna which operated at 915 MHz, and one or two fibreoptic thermometry probes for temperature measurement. Under fluoroscopic guidance the microwave antenna and temperature probes were positioned in the CT-determined tumour mass. The 60-min heat treatment achieved a central tumour temperature of 45-55 degrees C while keeping temperatures at the proximal and distal margins at 43 degrees C. Immediately following the hyperthermia treatment the microwave antenna and temperature probes were removed, and a single strand of iridium-192 double-strength seeds was inserted to irradiate the tumour length. A dose of 5500-7900 cGy calculated at 0.5 cm radially from the catheter was administered over 5-7 days. Upon removal of the iridium a second hyperthermia treatment was performed. A total of 18 hyperthermia treatments were administered to the 10 patients. In two cases the second hyperthermia treatment after brachytherapy was not possible due to a kink in the catheter, or bile precipitation in the catheter. All patients tolerated the procedure well, and there were no acute complications. To evaluate the volumetric heating potential of this hyperthermia method, specific absorption rate (SAR) values were measured at 182 planar points in muscle phantom. Insulated and non-insulated antenna performance was tested at 915 MHz in a biliary catheter filled with air, saline, or bile to mimic clinical treatments. The insulated antenna exhibited the best performance. Differences between antenna performance in saline and bile were also noted. In summary, this technique may have potential for tumours which obstruct biliary drainage and are

  8. Scope and mechanism of the iridium-catalyzed cleavage of alkyl ethers with triethylsilane. (United States)

    Yang, Jian; White, Peter S; Brookhart, Maurice


    The cationic iridium pincer complex [(POCOP)Ir(H)(acetone)](+)[B(C(6)F(5))(4)](-) {1, POCOP = 2,6-[OP(tBu)(2)](2)C(6)H(3)} was found to be a highly active catalyst for the room-temperature cleavage and reduction of a wide variety of unactivated alkyl ethers including primary, secondary, and tertiary alkyl ethers as well as aryl alkyl ethers by triethylsilane. Mechanistic studies have revealed the full details of the catalytic cycle with the catalyst resting state(s) depending on the basicity of the alkyl ether. During the catalytic reduction of diethyl ether, cationic iridium silane complex, [(POCOP)Ir(H)(eta(1)-Et(3)SiH)](+)[B(C(6)F(5))(4)](-) (3), and Et(2)O are in rapid equilibrium with neutral dihydride, (POCOP)Ir(H)(2) (5) and diethyl(triethylsilyl)oxonium ion, [Et(3)SiOEt(2)](+)[B(C(6)F(5))(4)](-) (7), with 5 + 7 strongly favored. Species 7 has been isolated from the reaction mixture and fully characterized. The turnover-limiting step in this cycle is the reduction of 7 by the neutral dihydride 5. The relative rates of reduction of 7 by dihydride 5 and Et(3)SiH were determined to be approximately 30,000:1. In the cleavage of the less basic ethers anisole and EtOSiEt(3), the cationic iridium silane complex, 3, was found to be the catalyst resting state. The hydride reduction of the intermediate oxonium ion EtO(SiEt(3))(2)(+), 9, occurs via attack by Et(3)SiH. In the case of anisole, the intermediate PhMeOSiEt(3)(+), 10, is reduced by 5 and/or Et(3)SiH.

  9. Techniques for Achieving Zero Stress in Thin Films of Iridium, Chromium, and Nickel (United States)

    Broadway, David M.; O'Dell, Stephen L.; Ramsey, Brian D.; Weimer, Jeffrey


    We examine techniques for achieving zero intrinsic stress in thin films of iridium, chromium, and nickel deposited by magnetron sputter deposition. The intrinsic stress is further correlated to the microstructural features and physical properties such as surface roughness and optical density at a scale appropriate to soft X-ray wavelengths. The examination of the stress in these materials is motivated by efforts to advance the optical performance of light-weight X-ray space telescopes into the regime of sub-arcsecond resolution through various deposition techniques that rely on control of the film stress to values within 10-100 MPa. A characteristic feature of the intrinsic stress behavior in chromium and nickel is their sensitivity to the magnitude and sign of the intrinsic stress with argon gas pressure and deposition rate, including the existence of a critical argon process pressure that results in zero film stress which scales linearly with the atomic mass of the sputtered species. While the effect of stress reversal with argon pressure has been previously reported by Hoffman and others for nickel and chromium, we report this effect for iridium. In addition to stress reversal, we identify zero stress in the optical functioning iridium layer shortly after island coalescence for low process pressures at a film thickness of approximately 35nm. The measurement of the low values of stress during deposition was achieved with the aid of a sensitive in-situ instrument capable of a minimum detectable level of stress, assuming a 35nm thick film, in the range of 0.40-6.0 MPa for oriented crystalline silicon substrate thicknesses of 70-280 microns, respectively.

  10. Efficient light harvesting and energy transfer in a red phosphorescent iridium dendrimer. (United States)

    Cho, Yang-Jin; Hong, Seong Ahn; Son, Ho-Jin; Han, Won-Sik; Cho, Dae Won; Kang, Sang Ook


    A series of red phosphorescent iridium dendrimers of the type [Ir(btp)2(pic-PCn)] (Ir-Gn; n = 0, 1, 2, and 3) with two 2-(benzo[b]thiophen-2-yl)pyridines (btp) and 3-hydroxypicolinate (pic) as the cyclometalating and ancillary ligands were prepared in good yields. Dendritic generation was grown at the 3 position of the pic ligand with 4-(9H-carbazolyl)phenyl dendrons connected to 3,5-bis(methyleneoxy)benzyloxy branches (PCn; n = 0, 2, 4, and 8). The harvesting photons on the PCn dendrons followed by efficient energy transfer to the iridium center resulted in high red emissions at ∼600 nm by metal-to-ligand charge transfer. The intensity of the phosphorescence gradually increased with increasing dendrimer generation. Steady-state and time-resolved spectroscopy were used to investigate the energy-transfer mechanism. On the basis of the fluorescence quenching rate constants of the PCn dendrons, the energy-transfer efficiencies for Ir-G1, Ir-G2, and Ir-G3 were 99, 98, and 96%, respectively. The energy-transfer efficiency for higher-generation dendrimers decreased slightly because of the longer distance between the PC dendrons and the core iridium(III) complex, indicating that energy transfer in Ir-Gn is a Förster-type energy transfer. Finally, the light-harvesting efficiencies for Ir-G1, Ir-G2, and Ir-G3 were determined to be 162, 223, and 334%, respectively.

  11. Mechanistic investigation of the iridium-catalysed alkylation of amines with alcohols

    DEFF Research Database (Denmark)

    Fristrup, Peter; Tursky, Matyas; Madsen, Robert


    , a line with a negative slope was obtained suggesting that nucleophilic attack on the aldehyde is selectivity-determining. A computational investigation of the entire catalytic cycle with full-sized ligands and substrates was performed using density functional theory. The results suggest a catalytic cycle...... where the intermediate aldehyde stays coordinated to the iridium catalyst and reacts with the amine to give a hemiaminal which is also bound to the catalyst. Dehydration to the imine and reduction to the product amine also takes place without breaking the coordination to the catalyst. The fact...

  12. RF Sputtered Iridium (Ir) Film as a Counter Electrode for Dye-Sensitized Solar Cells (United States)

    Mokurala, Krishnaiah; Kamble, Anvita; Bhargava, Parag; Mallick, Sudhanshu


    Iridium (Ir) films were deposited on fluorine-doped tin oxide substrate by radio-frequency sputtering at room temperature and the as-deposited films were used as counter electrodes (CE) for dye-sensitized solar cells (DSSC). The photo conversion efficiency (PCE) of DSSC fabricated with Ir-based CE was 7.2%. Electrocatalytic activity and electrochemical data for Ir-based CE were compared with those for conventional Pt-based CE. The results were indicative of potential use of Ir as an alternative CE material for DSSC.

  13. Stereodivergent Allylic Substitutions with Aryl Acetic Acid Esters by Synergistic Iridium and Lewis Base Catalysis. (United States)

    Jiang, Xingyu; Beiger, Jason J; Hartwig, John F


    The preparation of all possible stereoisomers of a given chiral molecule bearing multiple stereocenters by a simple and unified method is a significant challenge in asymmetric catalysis. We report stereodivergent allylic substitutions with aryl acetic acid esters catalyzed synergistically by a metallacyclic iridium complex and benzotetramisole. Through permutations of the enantiomers of the two chiral catalysts, all four stereoisomers of the products bearing two adjacent stereocenters are accessible with high diastereoselectivity and enantioselectivity. The resulting chiral activated ester products can be converted readily to enantioenriched amides, unactivated esters, and carboxylic acids in a one-pot manner.

  14. Iridium-catalyzed intermolecular dehydrogenative silylation of polycyclic aromatic compounds without directing groups. (United States)

    Murai, Masahito; Takami, Keishi; Takai, Kazuhiko


    This study describes the iridium-catalyzed intermolecular dehydrogenative silylation of C(sp(2))-H bonds of polycyclic aromatic compounds without directing groups. The reaction produced various arylsilanes through both Si-H and C-H bond activation, with hydrogen as the sole byproduct. Reactivity was affected by the electronic nature of the aromatic compounds, and silylation of electron-deficient and polycyclic aromatic compounds proceeded efficiently. Site-selectivity was controlled predominantly by steric factors. Therefore, the current functionalization proceeded with opposite chemo- and site-selectivity compared to that observed for general electrophilic functionalization of aromatic compounds.

  15. Application of P,N-sulfinyl imine ligands to iridium-catalyzed asymmetric hydrogenation of olefins. (United States)

    Schenkel, Laurie B; Ellman, Jonathan A


    The utility of a novel class of P,N-ligands incorporating a chiral sulfinyl imine moiety is demonstrated in the iridium-catalyzed hydrogenation of both functionalized and unfunctionalized olefins, in which enantioselectivities of up to 94% are achieved. The modularity of the P,N-sulfinyl ligand class is highlighted by the facile preparation of a variety of sterically and electronically different ligands. Interesting structure-activity data for both the phosphine and sulfinamide components is provided by this expanded ligand set.

  16. Chlorido(η4-1,5-cyclooctadiene[(pentafluoroethyldiphenylphosphane]iridium(I

    Directory of Open Access Journals (Sweden)

    Russell G. Baughman


    Full Text Available The title structure,[IrCl(C8H12(C14H10F5P], reveals that (C2F5PPh2 (pentafluoroethyldiphenylphosphane or pfepp disrupts the iridium dimer [(codIrCl]2 (cod = cycloocta-1,5-diene by rupturing the bridging chloride ligands and binding in the open coordination site to form (codIr(pfeppCl with the IrI atom in a distorted square-planar coordination environment. The structure deviates very little from the IrI–triphenylphosphine analog, although a significantly (∼20σ shorter Ir—P bond is noted for the title compound.

  17. Preparation of boron doped diamond modified by iridium for electroreduction of carbon dioxide (CO2) (United States)

    Ichzan, A. M.; Gunlazuardi, J.; Ivandini, T. A.


    Electroreduction of carbon dioxide (CO2) at iridium oxide-modified boron-doped diamond (IrOx-BDD) electrodes in aqueous electrolytes was studied by voltammetric method. The aim of this study was to find out the catalytic effect of IrOx to produce fine chemicals contained of two or more carbon atoms (for example acetic acid) in high percentage. Characterization using FE-SEM and XPS indicated that IrO2 can be deposited at BDD electrode, whereas characterization using cyclic voltammetry indicated that the electrode was applicable to be used as working electrode for CO2 electroreduction.

  18. The Collision of Iridium 33 and Cosmos 2251: The Shape of Things to Come (United States)

    Nicholas, Johnson


    The collision of Iridium 33 and Cosmos 2251 was the most severe accidental fragmentation on record. More than 1800 debris approx. 10 cm and larger were produced. If solar activity returns to normal, half of the tracked debris will reenter within five years. Less than 60 cataloged debris had reentered by 1 October 2009. Some debris from both satellites will remain in orbit through the end of the century. The collision rate of one every five years will increase without future removal of large derelict spacecraft and launch vehicle orbital stages.

  19. Sizeable Kane-Mele-like spin orbit coupling in graphene decorated with iridium clusters (United States)

    Qin, Yuyuan; Wang, Siqi; Wang, Rui; Bu, Haijun; Wang, Xuefeng; Wang, Xinran; Song, Fengqi; Wang, Baigeng; Wang, Guanghou


    The spin-orbit coupling strength of graphene can be enhanced by depositing iridium nanoclusters. Weak localization is intensely suppressed near zero fields after the cluster deposition, rather than changing to weak anti-localization. Fitting the magnetoresistance gives the spin relaxation time, which increases by two orders with the application of a back gate. The spin relaxation time is found to be proportional to the electronic elastic scattering time, demonstrating the Elliot-Yafet spin relaxation mechanism. A sizeable Kane-Mele-like coupling strength of over 5.5 meV is determined by extrapolating the temperature dependence to zero.

  20. Development of low-stress Iridium coatings for astronomical x-ray mirrors (United States)

    Döhring, Thorsten; Probst, Anne-Catherine; Stollenwerk, Manfred; Wen, Mingwu; Proserpio, Laura


    Previously used mirror technologies are not suitable for the challenging needs of future X-ray telescopes. This is why the required high precision mirror manufacturing triggers new technical developments around the world. Some aspects of X-ray mirrors production are studied within the interdisciplinary project INTRAAST, a German acronym for "industry transfer of astronomical mirror technologies". The project is embedded in a cooperation of Aschaffenburg University of Applied Sciences and the Max-Planck-Institute for extraterrestrial Physics. One important task is the development of low-stress Iridium coatings for X-ray mirrors based on slumped thin glass substrates. The surface figure of the glass substrates is measured before and after the coating process by optical methods. Correlating the surface shape deformation to the parameters of coating deposition, here especially to the Argon sputtering pressure, allows for an optimization of the process. The sputtering parameters also have an influence on the coating layer density and on the micro-roughness of the coatings, influencing their X-ray reflection properties. Unfortunately the optimum coating process parameters seem to be contrarious: low Argon pressure resulted in better micro-roughness and higher density, whereas higher pressure leads to lower coating stress. Therefore additional measures like intermediate coating layers and temperature treatment will be considered for further optimization. The technical approach for the low-stress Iridium coating development, the experimental equipment, and the obtained first experimental results are presented within this paper.

  1. Fabrication of iridium oxide nanoparticles supported on activated carbon powder by flashlight irradiation for oxygen evolutions

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dong-Hyun; Park, Sung-Hyeon [School of Mechanical Engineering, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of); Choi, Jinseong; Yi, Mi Hye [Eco Technology Center of the Hyundai Motor Company, 17-5 Mabuk-ro, Giheung-gu, Youngin-si, Gyeonggi-do 446-716 (Korea, Republic of); Kim, Hak-Sung, E-mail: [School of Mechanical Engineering, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791 (Korea, Republic of); Institute of Nano Science and Technology, Hanyang University, Seoul 133-791 (Korea, Republic of)


    Graphical abstract: Iridium supported on activated carbon was oxidized by flashlight irradiation at room temperature in ambient condition. - Highlights: • Ir was oxidized by flashlight irradiation at room temperature in ambient condition. • The Pt–IrO{sub 2}/C has a higher net current density than those of Pt–Ir/C and Pt/C. • During the flashlight process, an activated carbon was not damaged. • Flashlight irradiation purified an activated carbon by removing contaminants. - Abstract: In this study, iridium oxide (IrO{sub 2}) nanoparticles supported on activated carbon were fabricated for oxygen evolutions using a flashlight irradiation process at room temperature under ambient conditions within a few milliseconds. The fabricated IrO{sub 2} nanoparticles were decorated on the activated carbon surface and enlarged to 3.51 nm as average diameter from an initial value of 1.54 nm. The fabricated IrO{sub 2} nanoparticles were characterized using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) analysis, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and linear sweep voltammetry (LSV) for the oxygen evolution reaction.

  2. Treatment of carcinoma of the penis by iridium 192 wire implant

    Energy Technology Data Exchange (ETDEWEB)

    Daly, N.J.; Douchez, J.; Combes, P.F.


    Since 1971, a group of 22 adult patients with squamous cell carcinoma of the penis have been treated by iridium 192 wire implants. There were 6 T1 tumors, 14 T2 tumors and 2 T3; only one patient (T3) presented with local failure after implant. Local necrosis occurred in 2 patients without local tumoral recurrence, but was sufficient enough to warrant amputation. Thus 19/22 (86%) patients were locally cured with penile conservation. In these patients the most frequent posttherapeutic complication is chronic urethral stenosis (9/19 patients, 47%) requiring repeated instrumental dilations. Four patients presented with initial inguinal mestastatic nodes; only one was cured by radiosurgical treatment. Among patients without metastatic nodes at the time of diagnosis, none had delayed metastatic nodes. Three patients died of nodal evolution, 5 patients died of intercurrent disease without evidence of disease and 14 are now alive and NED. It appears that iridium 192 wire implant is the most effective conservative treatment of invasive squamous cell carcinoma of the penis; however, these results confirm that no particular treatment is required for inguinal nodal areas for patients who initially present with no disease.

  3. Photoluminescence Lifetime Imaging of Newly Synthesized Proteins in Living Cells with Iridium-alkyne Probe. (United States)

    Zhang, Xinrong; Wang, Jinyu; Xue, Jie; Yan, Zihe; Zhang, Sichun; Qiao, Juan


    Designing probes for real-time imaging of dynamic processes in living cells is a continual challenge. Herein, a novel near-infrared photoluminescence probe with long lifetime was exploited for photoluminescence lifetime imaging (PLIM) based on an Iridium-alkyne complex. This probe offers benefits of desirable deep-red to NIR emission, long stokes shift, excellent cell penetration, low cytotoxicity and good resistance to photobleaching. To the best of our knowledge this is the first PLIM probe applicable to click reaction of Cu(I)-catalysed azide-alkyne cycloaddition with remarkable lifetime shifts of 414 ns before and after click reaction. The approach fully eliminates the background interference and well distinguishes the reacted probes from the unreacted probes, thus enabling the wash-free imaging of the newly synthesized proteins in single living cells. Based on the unique properties of the Iridium complexes, it is anticipated to be applied in more important issues in living cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Oxygen reduction behavior of rutile-type iridium oxide in sulfuric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Yoshinaga, Norihiro; Sugimoto, Wataru [Department of Fine Materials Engineering, Faculty of Textile Science and Technology, Shinshu University, 3-15-1 Tokida, Ueda 386-8567 (Japan); Takasu, Yoshio [Department of Fine Materials Engineering, Faculty of Textile Science and Technology, Shinshu University, 3-15-1 Tokida, Ueda 386-8567 (Japan)], E-mail:


    Two different forms of rutile-type iridium oxide catalysts were prepared: IrO{sub 2}-coated titanium plate electrocatalysts prepared by a dip-coating method (IrO{sub 2}/Ti) and iridium oxide nanoparticles (IrO{sub 2}) prepared by a wet method, the Adams fusion method. The catalytic behavior of the oxygen reduction reaction (ORR) was evaluated by cyclic voltammetry in 0.5 M H{sub 2}SO{sub 4} at 60 deg. C. Both catalysts were found to exhibit considerable activity for the ORR; however, the former oxide electrodes showed higher activity than the latter ones. All the IrO{sub 2}/Ti catalyst electrodes heat-treated at a temperature between 400 deg. C and 550 deg. C showed ca. 0.84 V (vs. RHE) of the onset potential for the ORR, E{sub ORR}, where the reduction current of oxygen had begun to be observed during the cathodic potential sweep of the test electrodes. It has been confirmed clearly that IrO{sub 2}, but neither metallic Ir nor the hydrated IrO{sub 2}, behaves as an active catalyst for the ORR in an acidic solution. It was also demonstrated that the enlargement of the surface area of the IrO{sub 2}/Ti with the help of lanthanum is effective for the enhancement of the catalytic activity in the reaction.

  5. Ligand exchange and redox processes in iridium triazolylidene complexes relevant to catalytic water oxidation. (United States)

    Petronilho, Ana; Llobet, Antoni; Albrecht, Martin


    Iridium(III) complexes containing a bidentate spectator ligand have emerged as powerful catalyst precursors for water oxidation. Here we investigate the initial steps of the transformation at the iridium center when using complex [IrCp*(pyr-trz)Cl] 1 (Cp* = pentamethylcyclopentadienyl, pyr-trz = 4-(2-pyridyl)-1,2,3-triazol-5-ylidene), a potent water oxidation catalyst precursor. Ligand exchange with water is facile and is reversed in the presence of chloride ions, while MeCN substitution is effective only from the corresponding aqua complex. A pKa of 8.3 for the aqua complex was determined, which is in agreement with strong electron donation from the triazolylidene ligand that is comparable to aryl anions. Evaluation of the pH-dependent oxidation process in aqueous media reveals two regimes (pH 4-8.5 and above pH 10.5) where proton-coupled electron transfer processes occur. These investigations will help to further optimize water oxidation catalysts and indicate that MeCN as a cosolvent has adverse effects for initiating water coordination in the oxidation process.

  6. High-Performance Computer Modeling of the Cosmos-Iridium Collision (United States)

    Olivier, S.

    This paper describes the application of a new, integrated modeling and simulation framework, encompassing the space situational awareness (SSA) enterprise, to the recent Cosmos-Iridium collision. This framework is based on a flexible, scalable architecture to enable efficient simulation of the current SSA enterprise, and to accommodate future advancements in SSA systems. In particular, the code is designed to take advantage of massively parallel computer systems available, for example, at Lawrence Livermore National Laboratory. We will describe the application of this framework to the recent collision of the Cosmos and Iridium satellites, including (1) detailed hydrodynamic modeling of the satellite collision and resulting debris generation, (2) orbital propagation of the simulated debris and analysis of the increased risk to other satellites (3) calculation of the radar and optical signatures of the simulated debris and modeling of debris detection with space surveillance radar and optical systems (4) determination of simulated debris orbits from modeled space surveillance observations and analysis of the resulting orbital accuracy, (5) comparison of these modeling and simulation results with Space Surveillance Network observations. We will also discuss the use of this integrated modeling and simulation framework to analyze the risks and consequences of future satellite collisions and to assess strategies for mitigating or avoiding future incidents, including the addition of new sensor systems, used in conjunction with the Space Surveillance Network, for improving space situational awareness.

  7. Establishment of the platinum-iridium kilogram mass standards at NMIJ after the Extraordinary Calibrations (United States)

    Mizushima, Shigeki; Fujii, Kenichi


    The Bureau International des Poids et Mesures has carried out calibrations of the platinum-iridium kilogram mass standards by referencing the international prototype of the kilogram for the first time since the third periodic verification of national prototypes of the kilogram was carried out in 1988-92. This calibration campaign was designated ‘Extraordinary Calibrations’ in the second phase, in which two platinum-iridium kilogram mass standards of the National Metrology Institute of Japan were calibrated with a standard uncertainty of 3.5 μg. By adding these new calibration data into our data sets from 1991, we established our mass unit with a standard uncertainty of 3.3 μg by least-squares analysis using an exponential model, which is useful for compensating for mass increase after cleaning the mass standards. Moreover, it was found that our established mass unit following the Extraordinary Calibrations shifted against our previously maintained mass unit by  -20.8 μg as of the beginning of 2015. The analysis with a linear model revealed that the amount of mass increase over time of some standards was significantly smaller than that suggested at the third periodic verification of national prototypes of the kilogram. The analysis with the exponential model gave an exponent of 0.217 with a standard uncertainty of 0.057. This suggests that the mass increase due to surface contamination cannot be explained by a diffusion-limited process.

  8. Luminescent cyclometalated iridium(Ⅲ) dipyridoquinoxaline indole complexes as biological probes

    Institute of Scientific and Technical Information of China (English)

    LO; Kenneth; Kam-Wing; LEUNG; Arthur; Ho-Hon


    Four luminescent cyclometalated iridium(Ⅲ) dipyridoquinoxaline complexes appended with an indole moiety [Ir(NC)2(NN)] (PF6) (HNC = 2-phenylpyridine, Hppy; NN = 2-(N-(2-(indole-3-acetamido)ethyl)aminocarbonyl)dipyrido[3,2-f:2′,3′-h]quinox- aline, dpqC2indole (1a), NN = 2-(N-(6-(indole-3-acetamido)hexyl)aminocarbonyl)dipyrido[3,2-f:2′,3′-h]quinoxaline, dpqC6indole (1b); HNC = 7,8-benzoquinoline, Hbzq, NN = dpqC2indole (2a), NN = dpqC6indole (2b)) have been synthesized and characterized. Upon irradiation, all the complexes displayed moderately intense and long-lived luminescence under ambient condi-tions and in 77 K glass. On the basis of the photophysical data, the emission of the complexes has been assigned to an excited state of triplet metal-to-ligand charge-transfer (3MLCT) ((dπ(Ir)→π*(NN)) character. Cyclic voltammetric studies revealed indole-based and iridium-based oxidations at ca. +1.10 V and +1.24 V vs. SCE, respectively, and ligand-based reductions at ca. -1.07 to-2.29 V vs. SCE. The interactions of the complexes with an indole-binding protein, bovine serum albumin (BSA), have been examined by emission titrations.

  9. Colorimetric and luminescent bifunctional iridium(III) complexes for the sensitive recognition of cyanide ions (United States)

    Chen, Xiudan; Wang, Huili; Li, Jing; Hu, Wenqin; Li, Mei-Jin


    Two new cyclometalated iridium(III) complexes [(ppy)2Irppz]Cl (1) and [(ppy)2Irbppz]Cl (2) (where ppy = 2-phenylpyridine, ppz = 4,7-phenanthrolino-5,6:5,6-pyrazine, bppz = 2.3-di-2-pyridylpyrazine), were designed and synthesized. The structure of [(ppy)2Irppz]Cl was determined by single crystal X-ray diffraction. Their photophysical properties were also studied. This kind of complexes could coordinate with Cu2 +, the photoluminescence (PL) of the complex was quenched, and the color changed from orange-red to green. The forming M-Cu (M: complexes 1 and 2) ensemble could be further utilized as a colorimetric and emission "turn-on" bifunctional detection for CN-, especially for complex 1-Cu2 + showed a high sensitivity toward CN- with a limit of diction is 97 nM. Importantly, this kind of iridium(III) complexes shows a unique recognition of cyanide ions over other anions which makes it an eligible sensing probe for cyanide ions.

  10. The kinetics and mechanism of the organo-iridium-catalysed enantioselective reduction of imines. (United States)

    Stirling, Matthew J; Sweeney, Gemma; MacRory, Kerry; Blacker, A John; Page, Michael I


    The iridium complex of pentamethylcyclopentadiene and (S,S)-1,2-diphenyl-N'-tosylethane-1,2-diamine is an effective catalyst for the asymmetric transfer hydrogenation of imine substrates under acidic conditions. Using the Ir catalyst and a 5 : 2 ratio of formic acid : triethylamine as the hydride source for the asymmetric transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline and its 6,7-dimethoxy substituted derivative, in either acetonitrile or dichloromethane, shows unusual enantiomeric excess (ee) profiles for the product amines. The reactions initially give predominantly the (R) enantiomer of the chiral amine products with >90% ee but which then decreases significantly during the reaction. The decrease in ee is not due to racemisation of the product amine, but because the rate of formation of the (R)-enantiomer follows first-order kinetics whereas that for the (S)-enantiomer is zero-order. This difference in reaction order explains the change in selectivity as the reaction proceeds - the rate formation of the (R)-enantiomer decreases exponentially with time while that for the (S)-enantiomer remains constant. A reaction scheme is proposed which requires rate-limiting hydride transfer from the iridium hydride to the iminium ion for the first-order rate of formation of the (R)-enantiomer amine and rate-limiting dissociation of the product for the zero-order rate of formation of the (S)-enantiomer.

  11. Performance of TCP Vegas, Bic and Reno Congestion Control Algorithms on Iridium Satellite Constellations

    Directory of Open Access Journals (Sweden)



    Full Text Available Satellite networking is different from wired or wireless networks. The behavior and the performance of TCP/IP in normal wireless network as well as in wired network are different from one another. The TCP/IP protocol was not designed to perform well over high-latency or noisy channels so its performance over satellite networks are totally different. Each satellite networks/constellations have different properties. The deployment height, motion, direction, link capacity – all differ from one satellite constellations to another. So, certainly the behavior of TCP/IP will considerably differ from one satellite constellations than another.The Performance of three different TCP Congestion algorithms, Vegas, Reno and Bic are taken for evaluation on the simulated satellite network Iridium and the performance of the three algorithms under the satellites constellation is measured using suitable metrics. It is observed that, irrespective of the high end to end delay, the behavior of TCP/IP under Satellite network is somewhat resembling a high latency wired network. TCP under satellite network is not like that of a mobile ADHOC network. The observation resulted that the overall performance of Vegas was good in Iridium constellations. These reasons should be explored for designing a better congestion control algorithm exclusively for Satellite Networks.

  12. Picosecond laser micromachining of nitinol and platinum-iridium alloy for coronary stent applications

    Energy Technology Data Exchange (ETDEWEB)

    Muhammad, N.; Whitehead, D.; Li, L. [University of Manchester, Laser Processing Research Centre, School of Mechanical, Aerospace and Civil Engineering, Manchester (United Kingdom); Boor, A.; Oppenlander, W. [Swiss Tec AG, Schaan, Principality of Liechtenstein (Liechtenstein); Liu, Z. [University of Manchester, Corrosion and Protection Centre, School of Materials, Manchester (United Kingdom)


    The demand for micromachining of coronary stents by means of industrial lasers rises quickly for treating coronary artery diseases, which cause more than one million deaths each year. The most widely used types of laser for stent manufacturing are Nd:YAG laser systems with a wavelength of 1064 nm with pulse lengths of 10{sup -3}-10{sup -2} seconds. Considerable post-processing is required to remove heat-affected zones (HAZ), and to improve surface finishes and geometry. Using a third harmonic laser radiation of picosecond laser (6 x 10{sup -12} s pulse duration) in UV range, the capability of the picosecond laser micromachining of nitinol and platinum-iridium alloy for coronary stent applications are presented. In this study dross-free cut of nitinol and platinum-iridium alloy tubes are demonstrated and topography analysis of the cut surface is carried out. The HAZ characteristics have been investigated by means of microscopic examinations and measurement of micro-hardness distribution near the cut zones. (orig.)

  13. Picosecond laser micromachining of nitinol and platinum-iridium alloy for coronary stent applications (United States)

    Muhammad, N.; Whitehead, D.; Boor, A.; Oppenlander, W.; Liu, Z.; Li, L.


    The demand for micromachining of coronary stents by means of industrial lasers rises quickly for treating coronary artery diseases, which cause more than one million deaths each year. The most widely used types of laser for stent manufacturing are Nd:YAG laser systems with a wavelength of 1064 nm with pulse lengths of 10-3-10-2 seconds. Considerable post-processing is required to remove heat-affected zones (HAZ), and to improve surface finishes and geometry. Using a third harmonic laser radiation of picosecond laser (6×10-12 s pulse duration) in UV range, the capability of the picosecond laser micromachining of nitinol and platinum-iridium alloy for coronary stent applications are presented. In this study dross-free cut of nitinol and platinum-iridium alloy tubes are demonstrated and topography analysis of the cut surface is carried out. The HAZ characteristics have been investigated by means of microscopic examinations and measurement of micro-hardness distribution near the cut zones.

  14. High-Performance Computer Modeling of the Cosmos-Iridium Collision

    Energy Technology Data Exchange (ETDEWEB)

    Olivier, S; Cook, K; Fasenfest, B; Jefferson, D; Jiang, M; Leek, J; Levatin, J; Nikolaev, S; Pertica, A; Phillion, D; Springer, K; De Vries, W


    This paper describes the application of a new, integrated modeling and simulation framework, encompassing the space situational awareness (SSA) enterprise, to the recent Cosmos-Iridium collision. This framework is based on a flexible, scalable architecture to enable efficient simulation of the current SSA enterprise, and to accommodate future advancements in SSA systems. In particular, the code is designed to take advantage of massively parallel, high-performance computer systems available, for example, at Lawrence Livermore National Laboratory. We will describe the application of this framework to the recent collision of the Cosmos and Iridium satellites, including (1) detailed hydrodynamic modeling of the satellite collision and resulting debris generation, (2) orbital propagation of the simulated debris and analysis of the increased risk to other satellites (3) calculation of the radar and optical signatures of the simulated debris and modeling of debris detection with space surveillance radar and optical systems (4) determination of simulated debris orbits from modeled space surveillance observations and analysis of the resulting orbital accuracy, (5) comparison of these modeling and simulation results with Space Surveillance Network observations. We will also discuss the use of this integrated modeling and simulation framework to analyze the risks and consequences of future satellite collisions and to assess strategies for mitigating or avoiding future incidents, including the addition of new sensor systems, used in conjunction with the Space Surveillance Network, for improving space situational awareness.

  15. Penetrating microelectrode arrays with low-impedance sputtered iridium oxide electrode coatings. (United States)

    Cogan, Stuart F; Ehrlich, Julia; Plante, Timothy D; Van Wagenen, Rick


    Sputtered iridium oxide (SIROF) is a candidate low-impedance coating for neural stimulation and recording electrodes. SIROF on planar substrates has exhibited a high charge-injection capacity and impedance suitable for indwelling cortical microelectrode applications. In the present work, the properties of SIROF electrode coatings deposited onto multi-shank penetrating arrays intended for intracortical and intraneural applications were examined. The charge-injection properties under constant current pulsing were evaluated for a range of pulsewidths and current densities using voltage transients to determine maximum potential excursions in an inorganic model of interstitial fluid at 37 degrees C. The charge-injection capacity of the SIROFs was significantly improved by the use of positive potential biasing in the interpulse period, but even without bias, the SIROFs reversibly inject higher charge than other iridium oxides or platinum. Typical deliverable charge levels of 25 to 160 nC/phase were obtained with 2000 mum(2) electrodes depending on pulsewidth and interpulse bias. Similar sized platinum electrodes could inject 3 to 8 nC/phase.

  16. Iridium-catalysed dehydrocoupling of aryl phosphine-borane adducts: synthesis and characterisation of high molecular weight poly(phosphinoboranes). (United States)

    Paul, Ursula S D; Braunschweig, Holger; Radius, Udo


    The thermal dehydrogenative coupling of aryl phosphine-borane adducts with iridium complexes bearing a bis(phosphinite) pincer ligand is reported. This catalysis produces high molecular weight poly(phosphinoboranes) [ArPH-BH2]n (Ar = Ph, (p)Tol, Mes). Furthermore, we investigated the reactivity of these pincer complexes towards primary phosphines and their respective borane adducts on a stoichiometric scale.

  17. Cationic heteroleptic cyclometalated iridium(III) complexes containing phenyl-triazole and triazole-pyridine clicked ligands

    NARCIS (Netherlands)

    Felici, M.; Contreras-Carballada, P.; Smits, J.M.M.; Nolte, R.J.M.; Williams, R.M.; De Cola, L.; Feiters, M.C.


    Novel heteroleptic iridium complexes containing the 1-substituted-4-phenyl-1H-1,2,3-triazole (phtl) cyclometalating ligand have been synthesized. The 3+2 Huisgen dipolar cycloaddition method (‘click’ chemistry) was utilized to prepare a class of bidentate ligands (phtl) bearing different substituent

  18. Base-Free Production of H-2 by Dehydrogenation of Formic Acid Using An Iridium-bisMETAMORPhos Complex

    NARCIS (Netherlands)

    Oldenhof, S.; de Bruin, B.; Lutz, M.; Siegler, M.A.; Patureau, F.W.; van der Vlugt, J.I.; Reek, J.N.H.


    An iridium complex based on a cooperative ligand that functions as an internal base is reported. This complex can rapidly and cleanly dehydrogenate formic acid in absence of external base, a reaction that is required if formic acid is to be exploited as an energy carrier (see scheme).

  19. Poly(dendrimers) with phosphorescent iridium(III) complex-based side chains prepared via ring-opening metathesis polymerization

    NARCIS (Netherlands)

    Lai, W.-Y.; Balfour, M.N.; Levell, J.W.; Bansal, A.K.; Burn, P.L.; Lo, S.-C.; Samuel, I.D.W.


    Phosphorescent poly(dendrimers) with a norbornene-derived backbone have been synthesized using ring-opening metathesis polymerization with the Grubbs III catalyst. The dendrimers are comprised of a heteroleptic iridium(III) complex core with two 2-phenylpyridyl ligands and a phenyltriazolyl ligand,

  20. Results of an Iridium-Based Data Communication System Providing Internet Access to Polar Expeditions (United States)

    Mohammad, A.; Frost, V.; Braaten, D.


    The Polar Radar for Ice Sheet Measurements (PRISM) Project at the University of Kansas has developed and field-tested a versatile communications system for use by researchers in high-latitude Polar Regions. The PRISM project is developing advanced intelligent remote sensing technology that involves radar systems, an autonomous rover, and communications systems to measure detailed ice sheet characteristics, and to determine bed conditions (frozen or wet) below active ice sheets in both Greenland and Antarctica. We also have a very strong public outreach and educational program aimed at K-12 educators and students that requires data, voice and video feeds from Polar field locations in near real time. Hence, PRISM requires a robust communications system for use in the field between a base camp and the mobile remote sensing system, and from the field back to the University of Kansas and onto the Internet. The communication system that has been developed is truly mobile and is relatively inexpensive. We initially considered various satellite services during the design phase of this project. The two feasible options for high-latitude locations were Iridium, with its low-bit-rate service (2.4 Kb/s), and Inmarsat/Intelsat with broadband service. We selected the Iridium option for testing and development because it provided coverage in both Antarctica and Greenland. To achieve higher capacity communications, the multilink point-to-point protocol (MLPPP) implemented in Linux was tuned to operate efficiently over the Iridium satellite system. This mechanism combines multiple channels to obtain a seamless data connection with a capacity equal to the sum of the individual link rates. We used four Iridium modems to obtain an aggregate capacity of about 9.6 Kb/s. Standard Internet protocols (TCP/IP) were then used to provide end-to-end connectivity. The communications system field experiments were conducted at the NorthGRIP ice core drilling camp in Greenland (75° 06' N, 42° 20

  1. Revisiting the collision risk with cataloged objects for the Iridium and COSMO-SkyMed satellite constellations (United States)

    Pardini, Carmen; Anselmo, Luciano


    After two decades of slightly declining growth rate, the population of cataloged objects around the Earth increased by more than 56% in just a couple of years, from January 2007 to February 2009, due to two collisions in space involving the catastrophic destruction of three intact satellites (Fengyun 1C, Cosmos 2251 and Iridium 33) in high inclination orbits. Both events had occurred in the altitude range already most affected by previous launch activity and breakups. In 2011 a detailed analysis had been carried out to analyze the consequences of these fragmentations, in particular concerning the evolution of the collision risk for the Iridium and COSMO-SkyMed satellite constellations. Five years after such first assessment, the cataloged objects environment affecting the two constellations was revisited to evaluate how the situation had evolved due to the varying contribution of the above mentioned breakup fragments and the space activities carried out in the meantime. Being distributed, at 778 km, over six nearly polar orbit planes separated by just 30° at the equator, the Iridium satellites represent a very good gauge for checking the evolution of the environment in the most critical low Earth region. In approximately five years, from May 2011 to June 2016, the average flux of cataloged objects on the Iridium satellites increased by about 14%, to 1.59×10-5 m-2 per year. The cataloged fragments of Fengyun 1C, Cosmos 2251 and Iridium 33 still accounted for, on average, 54% of the total flux. More than 39% of the latter was associated with the Fengyun 1C fragments, about 11% with the Cosmos 2251 fragments and less than 4% with the Iridium 33 fragments. Specifically concerning the mutual interaction among the Iridium 33 debris and the parent constellation, the progressive dispersion and rather fast decay of the fragments below the Iridium operational altitude, coupled with a slow differential plane precession and low average relative velocities with respect to

  2. Partially reduced iridium oxide clusters dispersed on titania as efficient catalysts for facile synthesis of dimethylformamide from CO2, H2 and dimethylamine. (United States)

    Bi, Qing-Yuan; Lin, Jian-Dong; Liu, Yong-Mei; Xie, Song-Hai; He, He-Yong; Cao, Yong


    A novel bifunctional catalyst based on partially reduced iridium oxide supported on TiO2 was found to be exceedingly efficient for the organic-solvent-free synthesis of dimethylformamide from CO2, H2 and dimethylamine.

  3. Origins of enantioselectivity during allylic substitution reactions catalyzed by metallacyclic iridium complexes. (United States)

    Madrahimov, Sherzod T; Hartwig, John F


    In depth mechanistic studies of iridium catalyzed regioselective and enantioselective allylic substitution reactions are presented. A series of cyclometalated allyliridium complexes that are kinetically and chemically competent to be intermediates in the allylic substitution reactions was prepared and characterized by 1D and 2D NMR spectroscopies and single-crystal X-ray difraction. The rates of epimerization of the less thermodynamically stable diastereomeric allyliridium complexes to the thermodynamically more stable allyliridium stereoisomers were measured. The rates of nucleophilic attack by aniline and by N-methylaniline on the isolated allyliridium complexes were also measured. Attack on the thermodynamically less stable allyliridium complex was found to be orders of magnitude faster than attack on the thermodynamically more stable complex, yet the major enantiomer of the catalytic reaction is formed from the more stable diastereomer. Comparison of the rates of nucleophilic attack to the rates of epimerization of the diastereomeric allyliridium complexes containing a weakly coordinating counterion showed that nucleophilic attack on the less stable allyliridium species is much faster than conversion of the less stable isomer to the more stable isomer. These observations imply that Curtin-Hammett conditions are not met during iridium catalyzed allylic substitution reactions by η(3)-η(1)-η(3) interconversion. Rather, these data imply that when these conditions exist for this reaction, they are created by reversible oxidative addition, and the high selectivity of this oxidative addition step to form the more stable diastereomeric allyl complex leads to the high enantioselectivity. The stereochemical outcome of the individual steps of allylic substitution was assessed by reactions of deuterium-labeled substrates. The allylic substitution was shown to occur by oxidative addition with inversion of configuration, followed by an outer sphere nucleophilic attack

  4. Electronic Structures and Spectroscopic Properties of a Novel Iridium (Ⅲ) Complex with an Ancillary Ligand 2- (4-Trifluoromethyl -2-Hydroxylphenyl)Benzothiazole

    Institute of Scientific and Technical Information of China (English)

    LEI Li-Ping; HAO Yu-Ying; FAN Wen-Hao; XU Sing-She


    Iridium (W) complexes with 2-phenylpyridine (ppy) have been demonstrated as a type of promising phosphorescence dopant in emitting layers of organic light emitting diodes (OLKDs). In most iridium (M) complexes, there exist the strong spin-orbit coupling between it-orbiteds of cyclometalated ligands and 5d orbitals of the centric iridium. We study a novel iridium (M) complex (ppy)2lr(4-TfmBTZ) with ppy as cyclometalated ligands and 2-(4-trifluoromcthyl-2-hydroxyIphenyl)benzothiazole (4-TfmBTZ) as an ancillary ligand using the Gaussian 03 program. The geometries, electronic structures and spectroscopic properties of this iridium (M) complex are investigated by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The results show that the spin-orbit coupling occurs not only between ppy and iridium atom but also between 4-TfmBTZ and iridium atom in this complex. The highest occupied molecular orbital is dominantly localized on the Ir atom and 4-TfmBTZ ligand, while the lowest unoccupied molecular orbital on 4-TfmBTZ ligand. The triplet lowest-lying transition is attributed to the Ir-to-4-TfmBTZ charge-transfer ^MLCT) transition while the sub-low-lying transitions are assigned to the AMLCT transitions oflr(ppy)I. The nature of the lowest unoccupied orbital changes from ppy-localizcd to 4-TfmBTZ-locaIized and reveals that phosphorescent color oflr(M) complex can be controlled by the ancillary ligand and substitucnt.%@@ Iridium (Ⅲ) complexes with 2-phenylpyridine (ppy) have been demonstrated as a type of promising phospho- rescence dopant in emitting layers of organic light emitting diodes (OLEI)s).In most iridium (Ⅲ) complexes, there exist the strong spin-orbit coupling between π-orbitals of cyclometalated ligands anti 5d orbitals of the ccntric iridium.We study a novel iridium (Ⅲ) complex (ppy)2Ir(4-TfmBTZ) with ppy as cyclometalated ligands and 2-(4-trifluoromethyl-2-hydroxylphenyl)benzothiazole (4-TfmBTZ) as an ancillary ligand

  5. Distortion/interaction analysis reveals the origins of selectivities in iridium-catalyzed C-H borylation of substituted arenes and 5-membered heterocycles


    Green, AG; Liu, P.; Merlic, CA; Houk, KN


    The iridium-catalyzed borylation of mono- and disubstituted arenes and heteroarenes has been studied with density functional theory. The distortion/interaction model was employed to understand the origins of selectivities in these reactions. Computations revealed that the transition states for C-H oxidative addition are very late, resembling the aryl iridium hydride intermediate with a fully formed Ir-C bond. Consequently, the regioselectivity is mainly controlled by differences in the intera...

  6. Chemostratigraphy across the Cretaceous-Tertiary boundary and a critical assessment of the iridium anomaly

    Energy Technology Data Exchange (ETDEWEB)

    Tredoux, M.; De Wit, M.J.; Hart, R.J.; Lindsay, N.M.; Verhagen, B.; Sellschop, J.P.F. (Univ. of the Witwatersrand, Johannesburg (South Africa))


    The elevated concentration of iridium--one of the platinum-group elements (PGE)--at the Cretaceous-Tertiary boundary is still the most generally accepted evidence that a large bolide struck the earth at the time of the end-Cretaceous mass extinctions. New chemostratigraphic data for cross-boundary sections from both hemispheres are not easily explained in terms of such an impact event, for example the observation that the PGE patterns show marked differences between the hemispheres. The new constraints indicate that models of mantle-derived PGE should be seriously considered, and that PGE anomalies might not be as useful as previously thought as unambiguous identifiers of large impact events in the earth's history.

  7. Ascent of dinosaurs linked to an iridium anomaly at the Triassic-Jurassic boundary. (United States)

    Olsen, P E; Kent, D V; Sues, H-D; Koeberl, C; Huber, H; Montanari, A; Rainforth, E C; Fowell, S J; Szajna, M J; Hartline, B W


    Analysis of tetrapod footprints and skeletal material from more than 70 localities in eastern North America shows that large theropod dinosaurs appeared less than 10,000 years after the Triassic-Jurassic boundary and less than 30,000 years after the last Triassic taxa, synchronous with a terrestrial mass extinction. This extraordinary turnover is associated with an iridium anomaly (up to 285 parts per trillion, with an average maximum of 141 parts per trillion) and a fern spore spike, suggesting that a bolide impact was the cause. Eastern North American dinosaurian diversity reached a stable maximum less than 100,000 years after the boundary, marking the establishment of dinosaur-dominated communities that prevailed for the next 135 million years.

  8. Iridium-catalyzed asymmetric ring-opening of oxabenzonorbornadienes with phenols. (United States)

    Cheng, Hanchao; Yang, Dingqiao


    A novel iridium-catalyzed asymmetric ring-opening (ARO) reaction of oxabenzonorbornadienes with a variety of phenols was reported, which afforded the corresponding trans-2-phenoxy-1,2-dihydronaphthalen-1-ol products in high yields with moderate to excellent enantioselectivities (up to 98% ee) under mild conditions. The trans products are formed via the enantioselective cleavage of a bridgehead carbon-oxygen bond in 1 followed by S(N)2 nucleophilic attack by phenols. The effects of various bisphosphine ligands, Ag (I) salts, ammonium halides, bases, and solvents on the yield and enantioselectivity of the reaction were also investigated. The trans-configuration of the product 2a was confirmed by X-ray crystal structure analysis. A possible mechanism for the present catalytic reaction was proposed.

  9. Spin-orbit coupled jeff=1 /2 iridium moments on the geometrically frustrated fcc lattice (United States)

    Cook, A. M.; Matern, S.; Hickey, C.; Aczel, A. A.; Paramekanti, A.


    Motivated by experiments on the double perovskites La2ZnIrO6 and La2MgIrO6 , we study the magnetism of spin-orbit coupled jeff=1 /2 iridium moments on the three-dimensional, geometrically frustrated, face-centered cubic lattice. The symmetry-allowed nearest-neighbor interaction includes Heisenberg, Kitaev, and symmetric off-diagonal exchange. A Luttinger-Tisza analysis shows a rich variety of orders, including collinear A -type antiferromagnetism, stripe order with moments along the {111 } direction, and incommensurate noncoplanar spirals, and we use Monte Carlo simulations to determine their magnetic ordering temperatures. We argue that existing thermodynamic data on these iridates underscores the presence of a dominant Kitaev exchange, and also suggest a resolution to the puzzle of why La2ZnIrO6 , but not La2MgIrO6 , exhibits "weak" ferromagnetism.

  10. Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality. (United States)

    Arthurs, Ross A; Ismail, Muhammad; Prior, Christopher C; Oganesyan, Vasily S; Horton, Peter N; Coles, Simon J; Richards, Christopher J


    Reaction of [IrCp*Cl2 ]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6 H4 ) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp *,RIr *. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc ,Sp ,RIr . Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate.

  11. Iridium Oxide Nanotube Electrodes for Highly Sensitive and Prolonged Intracellular Measurement of Action Potentials (United States)

    Lin, Ziliang Carter; Xie, Chong; Osakada, Yasuko; Cui, Yi; Cui, Bianxiao


    Intracellular recording of action potentials is important to understand electrically-excitable cells. Recently, vertical nanoelectrodes have been developed to achieve highly sensitive, minimally invasive, and large scale intracellular recording. It has been demonstrated that the vertical geometry is crucial for the enhanced signal detection. Here we develop nanoelectrodes made up of nanotubes of iridium oxide. When cardiomyocytes are cultured upon those nanotubes, the cell membrane not only wraps around the vertical tubes but also protrudes deep into the hollow center. We show that this geometry enhances cell-electrode coupling and results in measuring much larger intracellular action potentials. The nanotube electrodes afford much longer intracellular access and are minimally invasive, making it possible to achieve stable recording up to an hour in a single session and more than 8 days of consecutive daily recording. This study suggests that the electrode performance can be significantly improved by optimizing the electrode geometry. PMID:24487777

  12. Operando study of iridium acetylacetonate decomposition on amorphous silica-alumina for bifunctional catalyst preparation. (United States)

    Nassreddine, Salim; Bergeret, Gérard; Jouguet, Bernadette; Geantet, Christophe; Piccolo, Laurent


    The decomposition of iridium acetylacetonate Ir(acac)(3) impregnated on amorphous silica-alumina (ASA) has been investigated by combined thermogravimetry-differential thermal analysis-mass spectrometry (TG-DTA-MS) and by in situ X-ray diffraction (XRD). The resulting Ir/ASA hydrotreating catalysts have also been characterized by transmission electron microscopy (TEM). The effects of heating treatments under oxidative, reductive or inert gas flows are compared with each other and with similar experiments on ASA-supported acetylacetone (acacH). It is shown that Ir(acac)(3) undergoes exothermic combustion during calcination in air, leading to agglomerated IrO(2) particles. Conversely, direct reduction involves hydrogenolysis of the acac followed by hydrogenation of the ligand residues to alkanes and water. These two processes are catalyzed by Ir clusters, the gradual growth of which is followed in situ by XRD. The resulting nanoparticles are highly and homogeneously dispersed.

  13. Half-sandwich ruthenium, rhodium and iridium complexes of triazolopyridine ligand: Synthesis and structural studies

    Indian Academy of Sciences (India)



    Triazolopyridine ligand, {3-(2-pyridyl)-[1,2,3]triazolo[1,5-a]-pyridine}, L was synthesized by reaction of p-toulenesulphonyl hydrazine and dipyridyl ketone in the presence of acetic acid. Half-sandwich ruthenium, rhodium and iridium complexes [1–4] have been synthesized by reaction of [{(arene)MCl₂}₂] (arene= p-cymene/benzene/Cp* and M = Ru/Rh/Ir) with ligand L in methanol. The reaction in 1:2 (M:L) ratio has yielded all mononuclear cationic complexes such as [(arene)MLκ²N∩N Cl]PF₆, where {(arene)M} = (p-cym)Ru(1), (benz)Ru (2), Cp*Rh (3) and Cp*Ir (4). All the complexes were characterized by spectral studies and the solid state structures of complexes, 1 and 3 were unambiguously determined by crystallographic studies.

  14. Nuclear moments of neutron-deficient iridium isotopes from laser spectroscopy

    CERN Document Server

    Verney, D; Cabaret, L A; Crawford, J; Duong, H T; Genevey, J; Huber, G; Ibrahim, F; Krieg, M; Lee, J K P; Lunney, M D; Obert, J; Oms, J; Pinard, J; Putaux, J C; Roussière, B; Sauvage, J; Sebastian, V


    Laser spectroscopy measurements have been performed on neutron- deficient iridium isotopes. The hyperfine structure and isotope shift of the optical Ir I transition 5d/sup 7/6s/sup 2/ /sup 4/F/sub 9/2/ to 5d/sup 7/6s6p /sup 6/F/sub 11/2/ at 351.5 nm have been studied for the /sup 182-189/Ir, /sup 186/Ir/sup m/ and /sup 191,193/Ir isotopes. The nuclear magnetic and quadrupole moments were obtained from the HFS measurements and the changes of the mean square charge radii from the IS measurements. A large mean square charge radius change between /sup 187/Ir and /sup 186/Ir and between /sup 186/Ir/sup m/ and /sup 186/Ir/sup g/ has been observed. (18 refs).

  15. Cationic iridium(III) complexes with two carbene-based cyclometalating ligands: cis versus trans isomers. (United States)

    Monti, Filippo; La Placa, Maria Grazia I; Armaroli, Nicola; Scopelliti, Rosario; Grätzel, Michael; Nazeeruddin, Mohammad Khaja; Kessler, Florian


    A series of cationic iridium(III) complexes with two carbene-based cyclometalating ligands and five different N^N bipyridine and 1,10-phenanthroline ancillary ligands is presented. For the first time--in the frame of a rarely studied class of bis(heteroleptic) iridium complexes with two carbene-based cyclometalating ligands--a pair of cis and trans isomers has been isolated. All complexes (trans-1-5 and cis-3) were characterized by (1)H NMR, (13)C NMR, (31)P NMR, and HRMS (ESI-TOF); in addition, crystal structures of cis-3 and trans-4 are reported and discussed. Cyclic voltammetric studies show that the whole series exhibits highly reversible oxidation and reduction processes, suggesting promising potential for optoelectronic applications. Ground-state DFT and TD-DFT calculations nicely predict the blue shift experimentally observed in the room-temperature absorption and emission spectra of cis-3, compared to the trans complexes. In CH3CN, cis-3 displays a 4-fold increase in photoluminescence quantum yield (PLQY) with respect to trans-3, as a consequence of drastically slower nonradiative rate constant. By contrast, at 77 K, the emission properties of all the compounds, including the cis isomer, are much more similar, with a pronounced hypsochromic shift for the trans complexes. A similar behavior is found in solid state (1% w/w poly(methyl methacrylate) matrix), with all complexes displaying PLQY of ∼70-80%, comparable emission lifetimes (τ ≈ 1.3 μs), and a remarkable rigidochromic shift. To rationalize the more pronounced nonradiative deactivation (and smaller PLQY) observed for photoexcited trans complexes, comparative temperature-dependent emission studies in the range of 77-450 K for cis-3 and trans-3 were made in propylene glycol, showing that solvation effects are primarily responsible for the observed behavior.

  16. Iridium-catalyzed enantioselective hydrogenation of imines in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Kainz, S.; Brinkmann, A.; Leitner, W.; Pfaltz, A.


    Supercritical carbon dioxide (scCO{sub 2}) was shown to be a reaction medium with unique properties for highly efficient iridium-catalyzed enantioselective hydrogenation of prochiral imines. Cationic iridium(I) complexes with chiral phosphinodihydrooxazoles, modified with perfluoroalkyl groups in the ligand or in the anion, were synthesized and tested in the hydrogenation of N-(1-phenylethylidene)aniline. Both the side chains and the lipophilic anions increased the solubility, but the choice of the anion also had a dramatic effect on the enantioselectivity with tetrakis-3,5-bis(trifluoromethyl)phenylborate (BARF) leading to the highest asymmetric induction. (R)-N-phenyl-1-phenylethylamine was formed quantitatively within 1 h in scCO{sub 2}[d(CO{sub 2}) = 0.75 g mL{sup {minus}1}] at 40 C and a H{sub 2} pressure of 30 bar with enantiomeric excesses of up to 81% using 0.078 mol % catalyst. The use of scCO{sub 2} instead of conventional solvents such as CH{sub 2}Cl{sub 2} allowed the catalyst loading to be lowered significantly owing to a change in the rate profile of the reaction. the homogeneous nature of the catalytically active species under the reaction conditions was demonstrated and was found to depend strongly on the composition of the reaction mixture and especially on the presence of the substrate. Utilizing the selective extractive properties of scCO{sub 2}, the product could be readily separated from the catalyst, which could be recycled several times without significant loss of activity and enantioselectivity. High-pressure FT-IR and NMR investigations revealed that the reactivity of the products to form the corresponding carbamic acids plays an important role for the application of this new methodology.

  17. Sol-Gel Deposition of Iridium Oxide for Biomedical Micro-Devices

    Directory of Open Access Journals (Sweden)

    Cuong M. Nguyen


    Full Text Available Flexible iridium oxide (IrOx-based micro-electrodes were fabricated on flexible polyimide substrates using a sol-gel deposition process for utilization as integrated pseudo-reference electrodes for bio-electrochemical sensing applications. The fabrication method yields reliable miniature on-probe IrOx electrodes with long lifetime, high stability and repeatability. Such sensors can be used for long-term measurements. Various dimensions of sol-gel iridium oxide electrodes including 1 mm × 1 mm, 500 µm × 500 µm, and 100 µm × 100 µm were fabricated. Sensor longevity and pH dependence were investigated by immersing the electrodes in hydrochloric acid, fetal bovine serum (FBS, and sodium hydroxide solutions for 30 days. Less pH dependent responses, compared to IrOx electrodes fabricated by electrochemical deposition processes, were measured at 58.8 ± 0.4 mV/pH, 53.8 ± 1.3 mV/pH and 48 ± 0.6 mV/pH, respectively. The on-probe IrOx pseudo-reference electrodes were utilized for dopamine sensing. The baseline responses of the sensors were higher than the one using an external Ag/AgCl reference electrode. Using IrOx reference electrodes integrated on the same probe with working electrodes eliminated the use of cytotoxic Ag/AgCl reference electrode without loss in sensitivity. This enables employing such sensors in long-term recording of concentrations of neurotransmitters in central nervous systems of animals and humans.

  18. Iridium anomaly in the cretaceous-paleogene boundary at Højerup (Stevns Klint, Denmark and Woodside Creek (New Zealand: The question of an enormous proportion of extraterrestrial component

    Directory of Open Access Journals (Sweden)

    Premović Pavle I.


    Full Text Available The Cretaceous-Paleogene boundary clays at Højerup and Woodside Creek show anomalous enrichments of iridium compared with the marine sedimentary rocks. For the average iridium content of 465 ppb in CI chondrite the estimate of the carbonaceous chondritic proportions in the decarbonated iridium-rich boundary layers, based on the integrated iridium fluencies, is about 26% at Højerup and 65% at Woodside Creek. These proportions are most likely too high due to a significant Ir influx from the nearby marine or continental site to these sections.

  19. Solution-processable deep red-emitting supramolecular phosphorescent polymer with novel iridium complex for organic light-emitting diodes (United States)

    Liang, Aihui; Huang, Gui; Wang, Zhiping; Wu, Wenjin; Zhong, Yu; Zhao, Shan


    A novel bis(dibenzo-24-crown-8)-functionalized iridium complex with an emission peak at 665 nm was synthesized. Several deep red-emitting supramolecualr phosphorescent polymers (SPPs) as a class of solutionprocessable electroluminescent (EL) emitters were formed by utilizing the efficient non-bonding self-assembly between the resulting iridium complex and bis(dibenzylammonium)-tethered monomers. These SPPs show an intrinsic glass transition with a T g of ca. 90 °C. The photophysical and electroluminescent properties are strongly dependent on the hosts' structures of the supramolecular phosphorescent polymers. The polymer light-emitting diode based on SPP3 displayed a maximal external quantum efficiency (EQE) of 2.14% ph·el-1 and the Commission Internationale de L'Eclairage (CIE) coordinates of (0.70, 0.29).

  20. Synthesis and crystal structure of the iridium(I) carbene complex with a pair of hydrogen wing tips (United States)

    Huang, H.-Y.; Chen, Z.-M.; Wang, Y.; Wu, E.-M.; Wang, G.; Jiang, M.-J.


    The iridium(I) cyclooctadiene complex with two (3- tert-butylimidazol-2-ylidene) ligands [(H-I m t Bu)2Ir(COD)]+PF 6 - (C22H32PF6IrN4) has been prepared, and its crystal structure is determined by X-ray diffraction. Complex exhibits slightly distorted square planar configurations around the metal atom, which is coordinated by two H-I m t Bu ligands and one cyclooctadiene group. The new iridium carbene complex has a pair of hydrogen wing tips. The Ir-Ccarbene bond lengths are 2.066(5) and 2.052(5) Å, and the bond angle C-Ir-C between these bonds is 95.54(19)°. The dihedral angle between two imidazol-2-ylidene rings is 86.42°.

  1. Supramolecular sky-blue phosphorescent polymer iridium complexes for single-emissive-layer organic light-emitting diodes. (United States)

    Liang, Ai-Hui; Dong, Sheng; Zhang, Kai; Xiao, Xiao; Huang, Fei; Zhu, Xu-Hui; Cao, Yong


    Novel supramolecular phosphorescent polymers (SPPs) are synthesized as a new class of solution-processable electroluminescent emitters. The formation of these SPPs takes advantage of the efficient non-bonding assembly between bis(dibenzo-24-crown-8)-functionalized iridium complex monomer and bis(dibenzylammonium)-tethered co-monomer, which is monitored by (1) H NMR spectroscopy and viscosity measurements. These SPPs show good film morphology and an intrinsic glass transition with a Tg of 94-116 °C. Noticeably, they are highly photoluminescent in solid state with quantum efficiency up to ca. 78%. The photophysical and electroluminescent properties are strongly dependent on the molecular structures of the iridium complex monomers.

  2. Influence of carbon, nitrogen and oxygen impurities on the ductility and electronic properties of fcc iridium: First-principles study (United States)

    Bannikov, V. V.; Shein, I. R.; Ivanovskii, A. L.


    Unusual changes in mechanical and electronic properties of fcc Ir in the presence of light sp elements (carbon, nitrogen and oxygen) as interstitial impurities have been predicted. By means of the ab initio calculations we found that, in contrast to the majority of other d metals, the ductility of iridium increases in the presence of the above impurities simultaneously with its "metallization" — owing to appreciable growth of the near-Fermi density of states.

  3. Secondary interactions or ligand scrambling? Subtle steric effects govern the iridium(I) coordination chemistry of phosphoramidite ligands. (United States)

    Osswald, Tina; Rüegger, Heinz; Mezzetti, Antonio


    The like and unlike isomers of phosphoramidite (P*) ligands are found to react differently with iridium(I), which is a key to explaining the apparently inconsistent results obtained by us and other research groups in a variety of catalytic reactions. Thus, the unlike diastereoisomer (aR,S,S)-[IrCl(cod)(1 a)] (2 a; cod=1,5-cyclooctadiene, 1 a=(aR,S,S)-(1,1'-binaphthalene)-2,2'-diyl bis(1-phenylethyl)phosphoramidite) forms, upon chloride abstraction, the monosubstituted complex (aR,S,S)-[Ir(cod)(1,2-eta-1 a,kappaP)](+) (3 a), which contains a chelating P* ligand that features an eta(2) interaction between a dangling phenyl group and iridium. Under analogous conditions, the like analogue (aR,R,R)-1 a' gives the disubstituted species (aR,R,R)-[Ir(cod)(1 a',kappaP)(2)](+) (4 a') with monodentate P* ligands. The structure of 3 a was assessed by a combination of X-ray and NMR spectroscopic studies, which indicate that it is the configuration of the binaphthol moiety (and not that of the dangling benzyl N groups) that determines the configuration of the complex. The effect of the relative configuration of the P* ligand on its iridium(I) coordination chemistry is discussed in the context of our preliminary catalytic results and of apparently random results obtained by other groups in the iridium(I)-catalyzed asymmetric allylic alkylation of allylic acetates and in rhodium(I)-catalyzed asymmetric cycloaddition reactions. Further studies with the unlike ligand (aS,R,R)-(1,1'-binaphthalene)-2,2'-diyl bis{[1-(1-naphthalene-1-yl)ethyl]phosphoramidite} (1 b) showed a yet different coordination mode, that is, the eta(4)-arene-metal interaction in (aS,R,R)-[Ir(cod)(1,2,3,4-eta-1 b,kappaP)](+) (3 b).

  4. Using iridium films to compensate for piezo-electric materials processing stresses in adjustable x-ray optics (United States)

    Ames, A.; Bruni, R.; Cotroneo, V.; Johnson-Wilke, R.; Kester, T.; Reid, P.; Romaine, S.; Tolier-McKinstry, S.; Wilke, R. H. T.


    Adjustable X-ray optics represent a potential enabling technology for simultaneously achieving large effective area and high angular resolution for future X-ray Astronomy missions. The adjustable optics employ a bimorph mirror composed of a thin (1.5 μm) film of piezoelectric material deposited on the back of a 0.4 mm thick conical mirror segment. The application of localized electric fields in the piezoelectric material, normal to the mirror surface, result in localized deformations in mirror shape. Thus, mirror fabrication and mounting induced figure errors can be corrected, without the need for a massive reaction structure. With this approach, though, film stresses in the piezoelectric layer, resulting from deposition, crystallization, and differences in coefficient of thermal expansion, can distort the mirror. The large relative thickness of the piezoelectric material compared to the glass means that even 100MPa stresses can result in significant distortions. We have examined compensating for the piezoelectric processing related distortions by the deposition of controlled stress chromium/iridium films on the front surface of the mirror. We describe our experiments with tuning the product of the chromium/iridium film stress and film thickness to balance that resulting from the piezoelectric layer. We also evaluated the repeatability of this deposition process, and the robustness of the iridium coating.

  5. Solvent-Dependent Structure of Iridium Dihydride Complexes: Different Geometries at Low and High Dielectricity of the Medium. (United States)

    Polukeev, Alexey V; Marcos, Rocío; Ahlquist, Mårten S G; Wendt, Ola F


    The hydride iridium pincer complex [(PCyP)IrH2] (PCyP=cis-1,3-bis[(di-tert-butylphosphino)methyl]cyclohexane, 1) reveals remarkably solvent-dependent hydride chemical shifts, isotope chemical shifts, JHD and T1(min), with rHH increasing upon moving to more polar medium. The only known example of such behaviour (complex [(POCOP)IrH2], POCOP=2,6-(tBu2PO)2C6H3) was explained by the coordination of a polar solvent molecule to the iridium (J. Am. Chem. Soc. 2006, 128, 17114). Based on the existence of an agostic bond between α-C-H and iridium in 1 in all solvents, we argue that the coordination of solvent can be rejected. DFT calculations revealed that the structures of 1 and [(POCOP)IrH2] depend on the dielectric permittivity of the medium and these compounds adopt trigonal-bipyramidal geometries in non-polar media and square-pyramidal geometries in polar media.

  6. Synthesis, structure, photophysical and electroluminescent properties of a blue-green self-host phosphorescent iridium(III) complex

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Jing; Wang, Hua [Key Laboratory of Interface Science and Engineering in Advanced Materials, Taiyuan University of Technology, Taiyuan 030024 (China); Xu, Huixia, E-mail: [Key Laboratory of Interface Science and Engineering in Advanced Materials, Taiyuan University of Technology, Taiyuan 030024 (China); Li, Jie; Wu, Yuling; Du, Xiaogang [Key Laboratory of Interface Science and Engineering in Advanced Materials, Taiyuan University of Technology, Taiyuan 030024 (China); Xu, Bingshe, E-mail: [Key Laboratory of Interface Science and Engineering in Advanced Materials, Taiyuan University of Technology, Taiyuan 030024 (China); College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024 (China)


    A kind of blue-green self-host phosphorescent iridium(III) complex, (CzPhBI){sub 2}Ir(tfmptz) [CzPhBI = 9-(6-(2-phenyl-1-benzimidazolyl)hexyl)-9-carbazole; tfmptz = 2-(5-trifluoromethyl-1,2,4-triazolyl)pyridine], was designed and synthesized. The synthesized iridium(III) complex was characterized by {sup 1}H NMR, {sup 19}F NMR, FT-IR, elemental analysis and X-ray single-crystal diffraction, respectively. Its thermal properties, optical properties and electrochemical properties were also investigated. The host-free organic electroluminescent devices with the configuration of ITO/MoO{sub 3} (3 nm)/NPB (30 nm)/TAPC (15 nm)/(CzPhBI){sub 2}Ir(tfmptz) (30 nm)/TBPI (30 nm)/LiF (1 nm)/Al (100 nm) had been fabricated. The devices exhibited excellent performance indicating that (CzPhBI){sub 2}Ir(tfmptz) was a promising phosphorescent material. - Highlights: • A blue-green self-host phosphorescent iridium(III) complex was synthesized. • The molecular structure, and photophysical properties were investigated. • Electroluminescent performance in host-free devices were discussed. • The maximum current efficiency 8.2 cd A{sup −1} and the maximum brightness 5420 cd m{sup −2} were achieved.

  7. Electronic Structures and Spectroscopic Properties of a Novel Iridium (III) Complex with an Ancillary Ligand 2-(4-Trifluoromethyl -2-Hydroxylphenyl) Benzothiazole (United States)

    Lei, Li-Ping; Hao, Yu-Ying; Fan, Wen-Hao; Xu, Bing-She


    Iridium (III) complexes with 2-phenylpyridine (ppy) have been demonstrated as a type of promising phosphorescence dopant in emitting layers of organic light emitting diodes (OLEDs). In most iridium (III) complexes, there exist the strong spin-orbit coupling between π-orbitals of cyclometalated ligands and 5d orbitals of the centric iridium. We study a novel iridium (III) complex (ppy)2Ir(4-TfmBTZ) with ppy as cyclometalated ligands and 2-(4-trifluoromethyl-2-hydroxylphenyl)benzothiazole (4-TfmBTZ) as an ancillary ligand using the Gaussian 03 program. The geometries, electronic structures and spectroscopic properties of this iridium (III) complex are investigated by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The results show that the spin-orbit coupling occurs not only between ppy and iridium atom but also between 4-TfmBTZ and iridium atom in this complex. The highest occupied molecular orbital is dominantly localized on the Ir atom and 4-TfmBTZ ligand, while the lowest unoccupied molecular orbital on 4-TfmBTZ ligand. The triplet lowest-lying transition is attributed to the Ir-to-4-TfmBTZ charge-transfer (3MLCT) transition while the sub-low-lying transitions are assigned to the 3MLCT transitions of Ir(ppy)2. The nature of the lowest unoccupied orbital changes from ppy-localized to 4-TfmBTZ-localized and reveals that phosphorescent color of Ir(III) complex can be controlled by the ancillary ligand and substituent.

  8. High-latitude poynting flux from combined Iridium and SuperDARN data

    Directory of Open Access Journals (Sweden)

    C. L. Waters


    Full Text Available Field-aligned currents convey stress between the magnetosphere and ionosphere, and the associated low altitude magnetic and electric fields reflect the flow of electromagnetic energy to the polar ionosphere. We introduce a new technique to measure the global distribution of high latitude Poynting flux, S||, by combining electric field estimates from the Super Dual Auroral Radar Network (SuperDARN with magnetic perturbations derived using magnetometer data from the Iridium satellite constellation. Spherical harmonic methods are used to merge the data sets and calculate S|| for any magnetic local time (MLT from the pole to 60° magnetic latitude (MLAT. The effective spatial resolutions are 2° MLAT, 2h MLT, and the time resolution is about one hour due to the telemetry rate of the Iridium magnetometer data. The technique allows for the assessment of high-latitude net S|| and its spatial distribution on one hour time scales with two key advantages: (1 it yields the net S|| including the contribution of neutral winds; and (2 the results are obtained without recourse to estimates of ionosphere conductivity. We present two examples, 23 November 1999, 14:00-15:00 UT, and 11 March 2000, 16:00-17:00 UT, to test the accuracy of the technique and to illustrate the distributions of S|| that it gives. Comparisons with in-situ S|| estimates from DMSP satellites show agreement to a few mW/m2 and in the locations of S|| enhancements to within the technique's resolution. The total electromagnetic energy flux was 50GW for these events. At auroral latitudes, S|| tends to maximize in the morning and afternoon in regions less than 5° in MLAT by two hours in MLT having S||=10 to 20mW/m2 and total power up to 10GW. The power poleward of the Region 1 currents is about one

  9. Study and development of an Iridium-192 seed for use in ophthalmic cancer; Estudo e desenvolvimento de uma semente de iridio-192 para aplicacao em cancer oftalmico

    Energy Technology Data Exchange (ETDEWEB)

    Mattos, Fabio Rodrigues de


    Even ocular tumors are not among the cases with a higher incidence, they affect the population, especially children. The Institute of Energy and Nuclear Research (IPEN-CNEN/SP) in partnership with Escola Paulista de Medicina (UNIFESP), created a project to develop and implement a alternative treatment for ophthalmic cancer that use brachytherapy iridium-192 seeds. The project arose by reason of the Escola Paulista treat many cancer cases within the Unified Health System (SUS) and the research experience of sealed radioactive sources group at IPEN. The methodology was developed from the available infrastructure and the experience of researchers. The prototype seed presents with a core (192-iridium alloy of iridium-platinum) of 3.0 mm long sealed by a capsule of titanium of 0.8 mm outside diameter, 0.05 mm wall thickness and 4,5mm long. This work aims to study and develop a seed of iridium-192 from a platinum-iridium alloy. No study on the fabrication of these seeds was found in available literature. It was created a methodology that involved: characterization of the material used in the core, creation of device for neutron activation irradiation and and seed sealing tests. As a result, proved the feasibility of the method. As a suggestion for future work, studies regarding metrology and dosimetry of these sources and improvement of the methodology should be carried out, for future implementation in national scope. (author)

  10. CO2 Hydrogenation Catalyzed by Iridium Complexes with a Proton-Responsive Ligand. (United States)

    Onishi, Naoya; Xu, Shaoan; Manaka, Yuichi; Suna, Yuki; Wang, Wan-Hui; Muckerman, James T; Fujita, Etsuko; Himeda, Yuichiro


    The catalytic cycle for the production of formic acid by CO2 hydrogenation and the reverse reaction have received renewed attention because they are viewed as offering a viable scheme for hydrogen storage and release. In this Forum Article, CO2 hydrogenation catalyzed by iridium complexes bearing sophisticated N^N-bidentate ligands is reported. We describe how a ligand containing hydroxy groups as proton-responsive substituents enhances the catalytic performance by an electronic effect of the oxyanions and a pendent-base effect through secondary coordination sphere interactions. In particular, [(Cp*IrCl)2(TH2BPM)]Cl2 (Cp* = pentamethylcyclopentadienyl; TH2BPM = 4,4',6,6'-tetrahydroxy-2,2'-bipyrimidine) enormously promotes the catalytic hydrogenation of CO2 in basic water by these synergistic effects under atmospheric pressure and at room temperature. Additionally, newly designed complexes with azole-type ligands were applied to CO2 hydrogenation. The catalytic efficiencies of the azole-type complexes were much higher than that of the unsubstituted bipyridine complex [Cp*Ir(bpy)(OH2)]SO4. Furthermore, the introduction of one or more hydroxy groups into ligands such as 2-pyrazolyl-6-hydroxypyridine, 2-pyrazolyl-4,6-dihydroxypyrimidine, and 4-pyrazolyl-2,6-dihydroxypyrimidine enhanced the catalytic activity. It is clear that the incorporation of additional electron-donating functionalities into proton-responsive azole-type ligands is effective for promoting further enhanced hydrogenation of CO2.

  11. Intracatheter hyperthermia and iridium-192 radiotherapy in the treatment of bile duct carcinoma. (United States)

    Wong, J Y; Vora, N L; Chou, C K; McDougall, J A; Chan, K W; Findley, D O; Forell, B W; Luk, K H; Philben, V J; Beatty, J D


    We report a case of a patient with locally advanced bile duct carcinoma treated with 4500 cGy external beam radiotherapy, followed 3 weeks later by intracatheter 915 MHz microwave hyperthermia and radiotherapy delivered through a biliary U-tube placed at the time of surgery. Heating was to 43-45 degrees C for 1 hour followed immediately by intracatheter Iridium-192 seeds to deliver 5000 cGy over a 72 hour period. Prior to treatment, a thermal dosimetry study in phanton was conducted, using the same type of U-tube catheter tubing as in the patient. Orthogonal X rays of the patient's porta hepatis region were used to reconstruct the catheter geometry in the phantom. Proper insertion depth was determined thermographically to obtain maximum heating at the center of the tumor. The maximum SAR was 8.8 watts per kilogram per watt input. During the treatment, the average power applied was 30 W. Six months after therapy, the patient is asymptomatic. Although alkaline phosphatase, SGOT and SGPT have remained elevated, bilirubin has returned to normal and computerized tomographic scans and cholangiograms remain stable. A duodenal ulcer developed after therapy and is healing well with conservative medical management. This case demonstrates that hyperthermia applied through biliary drainage catheters is technically feasible and clinically tolerated. We believe the use of intracatheter hyperthermia in conjunction with external and/or intracatheter radiotherapy in selected patients with unresectable bile duct carcinomas warrants further study.

  12. Preparation of platinum-iridium nanoparticles on titania nanotubes by MOCVD and their catalytic evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Colindres, S. Capula [National Polytechnic Institute, Department of Metallurgical Eng., Mexico 07300 D.F., AP 75-874 (Mexico); Garcia, J.R. Vargas, E-mail: rvargasga@ipn.m [National Polytechnic Institute, Department of Metallurgical Eng., Mexico 07300 D.F., AP 75-874 (Mexico); Antonio, J.A. Toledo; Chavez, C. Angeles [Petroleum Mexican Institute, Eje Central Lazaro Cardenas No.152, Mexico 07730 D.F. (Mexico)


    Pt based catalysts are commonly used in several industrial processes involving hydrogenation and dehydrogenation reactions. New deposition methods as well as support materials are being investigated to generate new catalysts with superior catalytic activity. In this work, platinum-iridium (Pt-Ir) nanoparticles of about 5 nm in size were supported on titania (TiO{sub 2}) nanotubes by metal organic chemical vapor deposition (MOCVD). The TiO{sub 2} nanotubes were prepared by an alkali hydrothermal method using sodium hydroxide solution at 100 deg. C, during 64.8 ks. Pt-Ir nanoparticles were obtained by controlling the MOCVD conditions at 400 deg. C and 66.6 kPa. Textural properties and particle size were investigated by nitrogen physisorption (BET method), X-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy. Catalytic activity was measured in cyclohexene disproportion as the test molecule for hydrogenation/dehydrogenation reactions. The TiO{sub 2} nanotubes exhibit a considerable high surface area of about 425,000 m{sup 2}/kg, however, after calcination at 400 deg. C their nanotubular morphology was partially transformed. In spite of this change, the 5 nm Pt-Ir nanoparticles supported on TiO{sub 2} nanotubes were more active in the cyclohexene disproportion reaction than conventional Pt-Ir/alumina catalysts in the whole range of temperatures investigated (50-250 deg. C). Hydrogenation reactions (high selectivity to cyclohexane) predominate at temperatures below 150 deg. C.

  13. Determination of the tissue inhomogeneity correction in high dose rate Brachytherapy for Iridium-192 source

    Directory of Open Access Journals (Sweden)

    Barlanka Ravikumar


    Full Text Available In Brachytherapy treatment planning, the effects of tissue heterogeneities are commonly neglected due to lack of accurate, general and fast three-dimensional (3D dose-computational algorithms. In performing dose calculations, it is assumed that the tumor and surrounding tissues constitute a uniform, homogeneous medium equivalent to water. In the recent past, three-dimensional computed tomography (3D-CT based treatment planning for Brachytherapy applications has been popularly adopted. However, most of the current commercially available planning systems do not provide the heterogeneity corrections for Brachytherapy dosimetry. In the present study, we have measured and quantified the impact of inhomogeneity caused by different tissues with a 0.015 cc ion chamber. Measurements were carried out in wax phantom which was employed to measure the heterogeneity. Iridium-192 (192 Ir source from high dose rate (HDR Brachytherapy machine was used as the radiation source. The reduction of dose due to tissue inhomogeneity was measured as the ratio of dose measured with different types of inhomogeneity (bone, spleen, liver, muscle and lung to dose measured with homogeneous medium for different distances. It was observed that different tissues attenuate differently, with bone tissue showing maximum attenuation value and lung tissue resulting minimum value and rest of the tissues giving values lying in between those of bone and lung. It was also found that inhomogeneity at short distance is considerably more than that at larger distances.

  14. Probing the Viability of Oxo-Coupling Pathways in Iridium-Catalyzed Oxygen Evolution. (United States)

    Graeupner, Jonathan; Hintermair, Ulrich; Huang, Daria L; Thomsen, Julianne M; Takase, Mike; Campos, Jesús; Hashmi, Sara M; Elimelech, Menachem; Brudvig, Gary W; Crabtree, Robert H


    A series of Cp*Ir(III) dimers have been synthesized to elucidate the mechanistic viability of radical oxo-coupling pathways in iridium-catalyzed O2 evolution. The oxidative stability of the precursors toward nanoparticle formation and their oxygen evolution activity have been investigated and compared to suitable monomeric analogues. We found that precursors bearing monodentate NHC ligands degraded to form nanoparticles (NPs), and accordingly their O2 evolution rates were not significantly influenced by their nuclearity or distance between the two metals in the dimeric precursors. A doubly chelating bis-pyridine-pyrazolide ligand provided an oxidation-resistant ligand framework that allowed a more meaningful comparison of catalytic performance of dimers with their corresponding monomers. With sodium periodate (NaIO4) as the oxidant, the dimers provided significantly lower O2 evolution rates per [Ir] than the monomer, suggesting a negative interaction instead of cooperativity in the catalytic cycle. Electrochemical analysis of the dimers further substantiates the notion that no radical oxyl-coupling pathways are accessible. We thus conclude that the alternative path, nucleophilic attack of water on high-valent Ir-oxo species, may be the preferred mechanistic pathway of water oxidation with these catalysts, and bimolecular oxo-coupling is not a valid mechanistic alternative as in the related ruthenium chemistry, at least in the present system.

  15. A theoretical study on small iridium clusters: structural evolution, electronic and magnetic properties, and reactivity predictors. (United States)

    Du, Jiguang; Sun, Xiyuan; Chen, Jun; Jiang, Gang


    The structural, electronic, and magnetic properties of iridium clusters with sizes of n = 2-15 are investigated by employing the generalized gradient approximation of density functional theory. Simple cube evolution pattern is revealed for Ir(2-15) clusters, as predicted by previous reports. It is remarkable that for Ir(10), Ir(11) clusters, new generated isomers with higher stabilities relative to those reported in previous studies are obtained. The even-sized clusters are more stable than the odd-sized species. The Ir-Ir bonds in the cubic Ir(8) and Ir(12) clusters, which are considered as the basic units in the structural evolution present covalent character. Starting from n = 8, the magnetic moments of Ir(n) clusters decrease sharply. The moments of magnetic clusters show 5d characters. The reactive site selectivity of studied clusters with n = 5-15 is analyzed with condensed Fukui function. The capped atoms in certain clusters (Ir(9), Ir(10), Ir(11), and Ir(13)) generally show extraordinary activity for both nucleophilic and electrophilic attack.

  16. Mechanistic investigation of the iridium-catalysed alkylation of amines with alcohols. (United States)

    Fristrup, Peter; Tursky, Matyas; Madsen, Robert


    The [Cp*IrCl(2)](2)-catalysed alkylation of amines with alcohols was investigated using a combination of experimental and theoretical methods. A Hammett study involving a series of para-substituted benzyl alcohols resulted in a line with a negative slope. This clearly documents that a positive charge is built up in the transition state, which in combination with the measurement of a significant kinetic isotope effect determines hydride abstraction as being the selectivity-determining step under these conditions. A complementary Hammett study using para-substituted anilines was also carried out. Again, a line with a negative slope was obtained suggesting that nucleophilic attack on the aldehyde is selectivity-determining. A computational investigation of the entire catalytic cycle with full-sized ligands and substrates was performed using density functional theory. The results suggest a catalytic cycle where the intermediate aldehyde stays coordinated to the iridium catalyst and reacts with the amine to give a hemiaminal which is also bound to the catalyst. Dehydration to the imine and reduction to the product amine also takes place without breaking the coordination to the catalyst. The fact that the entire catalytic cycle takes place with all the intermediates bound to the catalyst is important for the further development of this synthetic transformation.

  17. Synthesis, structure, redox and spectra of green iridium complexes of tridentate azo-aromatic ligands

    Indian Academy of Sciences (India)

    Manashi Panda; Chayan Das; Chen-Hsiung Hung; Sreebrata Goswami


    Reactions of IrCl3$\\cdot$ H2O with the ligands, 2-[(phenylamino)phenylazo]pyridine (HL1a) and 2-[(-tolylamino)phenylazo]pyridine (HL1b) produce [Ir(L1)2]Cl (L1 = L1a, [1]Cl and L1 = L1b, [2]Cl) along with many unidentified products. The iridium complexes have been characterized by various techniques such as X-ray crystallography, mass spectrometry, 1H and 13C NMR, cyclic voltammetry and absorption studies. The complex [1]ClO4 crystallises in triclinic space group. The crystallographic data have been determined. Notably, the Ir-N (azo) lengths are short (av. 1.9875(4) Å) as compared to the remaining four Ir-N lengths (av. 2.052(5) Å). There is significant degree of ligand backbone conjugation in the coordinated ligands, which result in shortening of the C-N lengths on the other side of the middle phenyl ring and also in lengthening of the diazo (N=N) lengths. The complexes display multiple low energy transitions ranging between 1010 and 450 nm. These are electro active and show three reversible redox responses in the potential range, +1.5 V to -1.5 V. The cathodic potential responses are ascribed as ligand reductions, while the redox process at the anodic potential occurs at a mixed metal-ligand (HOMO) orbital.

  18. Facile synthesis of iridium nanocrystals with well-controlled facets using seed-mediated growth. (United States)

    Xia, Xiaohu; Figueroa-Cosme, Legna; Tao, Jing; Peng, Hsin-Chieh; Niu, Guangda; Zhu, Yimei; Xia, Younan


    Iridium nanoparticles have only been reported with roughly spherical shapes and sizes of 1-5 nm, making it impossible to investigate their facet-dependent catalytic properties. Here we report for the first time a simple method based on seed-mediated growth for the facile synthesis of Ir nanocrystals with well-controlled facets. The essence of this approach is to coat an ultrathin conformal shell of Ir on a Pd seed with a well-defined shape at a relatively high temperature to ensure fast surface diffusion. In this way, the facets on the initial Pd seed are faithfully replicated in the resultant Pd@Ir core-shell nanocrystal. With 6 nm Pd cubes and octahedra encased by {100} and {111} facets, respectively, as the seeds, we have successfully generated Pd@Ir cubes and octahedra covered by Ir{100} and Ir{111} facets. The Pd@Ir cubes showed higher H2 selectivity (31.8% vs 8.9%) toward the decomposition of hydrazine compared with Pd@Ir octahedra with roughly the same size.

  19. Superconductivity in the ternary iridium-arsenide BaIr2As2 (United States)

    Wang, Xiao-Chuan; Ruan, Bin-Bin; Yu, Jia; Pan, Bo-Jin; Mu, Qing-Ge; Liu, Tong; Chen, Gen-Fu; Ren, Zhi-An


    Here we report the synthesis and discovery of superconductivity in a novel ternary iridium-arsenide compound BaIr2As2. The polycrystalline BaIr2As2 sample was first synthesized by a high temperature and high pressure method. Crystal structural analysis indicates that BaIr2As2 crystallizes in the ThCr2Si2-type layered tetragonal structure with space group I4/mmm (No. 139), and the lattice parameters were refined to be a = 4.052(9) Å and c = 12.787(8) Å. By the electrical resistivity and magnetic susceptibility measurements we found type-II superconductivity in the new BaIr2As2 compound with a T c (critical temperature) of 2.45 K, and an upper critical field μ 0 H c2(0) about 0.2 T. Low temperature specific heat measurements gave a Debye temperature of about 202 K and a distinct specific jump with ΔC e /γT c = 1.36, which is close to the value of BCS weak coupling limit and confirms the bulk superconductivity in this new BaIr2As2 compound.

  20. Small computer algorithms for comparing therapeutic performances of single-plane iridium implants. (United States)

    Murphy, D J; Doss, L L


    We present a uniform method for selecting an optimum implant geometry by presenting techniques for evaluating the therapeutically significant maximum dose rate (herein referred to as the "maximum dose rate"), the reference isodose (85% of the maximum dose rate), and the area enclosed by the reference isodose contour. The therapeutic performances of planar iridium implants may be compared by evaluating their respective maximum dose rates, reference isodoses , and areas within the reference isodose contours. Because these parameters are mathematically defined, they reproducibly describe each implant geometry. We chose a small microcomputer to develop these comparison algorithms so that the radiotherapist need not have large, expensive computer facilities available to conduct his own studies. The development of these algorithms led to some significant conclusions and recommendations regarding the placement of interstitial implants. Using seeds that are centrally located in the array to evaluate the maximum dose contour avoids underestimating the array's maximum dose rate. This could occur if edge or corner seeds were used. Underestimating the maximum dose rate (and hence the reference isodose contour area) may have a serious therapeutic outcome, because the actual total treatment dosage may be excessive. As ribbon spacing is increased, there is a point beyond which the reference isodose contours become decoupled. At this point, a single relatively uniform reference isodose contour separates into several contours. This effect not only complicates the planimetry calculations, but it also adversely affects the therapeutic efficacy of the implant by producing therapeutically "cold" regions.

  1. Electrical Characteristics and Nanocrystalline Formation of Sprayed Iridium Oxide Thin Films

    Directory of Open Access Journals (Sweden)

    S. A. Mahmoud


    Full Text Available Nanostructure and electrical properties of iridium oxide (IrO2 thin films prepared by spray pyrolysis technique (SPT have been experimentally characterized. The effect of solution molarity (SM and substrate temperature (sub on the nanostructure features and electrical conductivity of these films has been investigated. The results of X-ray diffraction (XRD showed that all samples prepared at sub=350∘C with different SM, IrO2 appear almost in amorphous form. XRD revealed that the films deposited at sub=450∘C were tetragonal structures with a preferential orientation along ⟨101⟩ direction. Moreover, the degree of crystallinity was improved by solution molarity. Single order Voigt profile method has been used to determine the nanostructure parameters at different SM and sub. The dark conductivity measurements at room temperature as a function of SM were observed and the value of conductivity were slightly increases at higher SM, reaching the bulk value of 20 Ω−1cm−1. The values of activation energy of Δ and of IrO2 were found to be 0.21 eV and 1.68×10−3Ω−1·cm−1, respectively.

  2. The Decomposition of Hydrazine in the Gas Phase and over an Iridium Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, Michael W. [Ames Laboratory; Gordon, Mark S. [Ames Laboratory


    Hydrazine is an important rocket fuel, used as both a monopropellant and a bipropellant. This paper presents theoretical results to complement the extensive experimental studies of the gas phase and Ir catalyzed decompositions involved in the monopropellant applications of hydrazine. Gas phase electronic structure theory calculations that include electron correlation predict that numerous molecular and free radical reactions occur within the same energy range as the basic free radical pathways: NN bond breaking around 65 kcal/mol and NH bond breaking around 81 kcal/mol. The data suggest that a revision to existing kinetics modeling is desirable, based on the energetics and the new elementary steps reported herein. A supported Ir-6 octahedron model for the Shell 405 Iridium catalyst used in thrusters was developed. Self-Consistent Field and electron correlation calculations (with core potentials and associated basis sets) find a rich chemistry for hydrazine on this catalyst model. The model catalyst provides dramatically lower NN and NH bond cleavage energies and an even smaller barrier to breaking the NH bond by NH2 abstractions. Thus, the low temperature decomposition over the catalyst is interpreted in terms of consecutive NH2 abstractions to produce ammonia and nitrogen. The higher temperature channel, which has hydrogen and nitrogen products, may be due to a mixture of two mechanisms. These two mechanisms are successive NH cleavages with surface H + H recombinations, and the same type of assisted H-2 eliminations found to occur in the gas phase part of this study.

  3. Iridium-catalysed regioselective borylation of carboranes via direct B-H activation (United States)

    Cheng, Ruofei; Qiu, Zaozao; Xie, Zuowei


    Carboranes are carbon-boron molecular clusters, which can be viewed as three-dimensional analogues to benzene. They are finding many applications in medicine, materials and organometallic chemistry. On the other hand, their exceptional thermal and chemical stabilities, as well as 3D structures, make them very difficult to be functionalized, in particular the regioselective functionalization of BH vertex among ten similar B-H bonds. Here we report a very efficient iridium-catalysed borylation of cage B(3,6)-H bonds of o-carboranes with excellent yields and regioselectivity using bis(pinacolato)diboron (B2pin2) as a reagent. Selective cage B(4)-H borylation has also been achieved by introducing a bulky TBDMS (tert-butyldimethylsilyl) group to one cage carbon vertex. The resultant 3,6-(Bpin)2-o-carboranes are useful synthons for the synthesis of a wide variety of B(3,6)-difunctionalized o-carboranes bearing cage B-X (X=O, N, C, I and Br) bonds.

  4. Versatile deprotonated NHC: C,N-bridged dinuclear iridium and rhodium complexes

    Directory of Open Access Journals (Sweden)

    Albert Poater


    Full Text Available Bearing the versatility of N-heterocyclic carbene (NHC ligands, here density functional theory (DFT calculations unravel the capacity of coordination of a deprotonated NHC ligand (pNHC to generate a doubly C2,N3-bridged dinuclear complex. Here, in particular the discussion is based on the combination of the deprotonated 1-arylimidazol (aryl = mesityl (Mes with [M(cod(μ-Cl] (M = Ir, Rh generated two geometrical isomers of complex [M(cod{µ-C3H2N2(Mes-κC2,κN3}]2. The latter two isomers display conformations head-to-head (H-H and head-to-tail (H-T of CS and C2 symmetry, respectively. The isomerization from the H-H to the H-T conformation is feasible, whereas next substitutions of the cod ligand by CO first, and PMe3 later confirm the H-T coordination as the thermodynamically preferred. It is envisaged the exchange of the metal, from iridium to rhodium, confirming here the innocence of the nature of the metal for such arrangements of the bridging ligands.

  5. Relation between emission properties and the surface composition of binary and ternary iridium base alloys

    Energy Technology Data Exchange (ETDEWEB)

    Gnuchev, N.M.; Gell, A.P.


    Changes in the surface composition and emission properties of iridium alloys with 1.8 and 2.7 at. % of cerium as well as Ir - 8% Ce - 5% Mo and Ir - 8% Ce - 15% Re in the process of thermal treatment in the temperature range of 1400-2000 K were studied. Thermoelectron work function and specimen Auger spectra were detected. The investigations were carried on by experimental instruments equipped with three-grid quasi-spherical analyzers of approximately 0.5% resolution. The investigations have shown that heating at 900-2000 K results in marked improvement of emission properties of both two-and three-component alloys. The surface is cleaned from contaminants and its elementary composition and structure reach optimal ones. At the same time intensive cerium evaporation occurs and emission capability of alloys of low cerium content drops at such high temperatures. So, heating of Ir - 1% Ce specimen during several hours at 2000 K resulted in reduction of cerium Auger peak amplitude and increase in work function by 0.3 eV.

  6. Iridium-catalysed regioselective borylation of carboranes via direct B–H activation (United States)

    Cheng, Ruofei; Qiu, Zaozao; Xie, Zuowei


    Carboranes are carbon–boron molecular clusters, which can be viewed as three-dimensional analogues to benzene. They are finding many applications in medicine, materials and organometallic chemistry. On the other hand, their exceptional thermal and chemical stabilities, as well as 3D structures, make them very difficult to be functionalized, in particular the regioselective functionalization of BH vertex among ten similar B–H bonds. Here we report a very efficient iridium-catalysed borylation of cage B(3,6)–H bonds of o-carboranes with excellent yields and regioselectivity using bis(pinacolato)diboron (B2pin2) as a reagent. Selective cage B(4)–H borylation has also been achieved by introducing a bulky TBDMS (tert-butyldimethylsilyl) group to one cage carbon vertex. The resultant 3,6-(Bpin)2-o-carboranes are useful synthons for the synthesis of a wide variety of B(3,6)-difunctionalized o-carboranes bearing cage B–X (X=O, N, C, I and Br) bonds. PMID:28300061

  7. Cationic iridium(III) complexes bearing a bis(triazole) ancillary ligand. (United States)

    Donato, Loïc; Abel, Philippe; Zysman-Colman, Eli


    Three new heteroleptic cationic iridium complexes of the form [Ir(C^N)(btl)](+), where btl = 1,1'-benzyl-4,4'-bi-1H-1,2,3-triazolyl and C^N = 2-phenylpyridine (ppyH) (1), 1-benzyl-4-phenyl-1H-1,2,3-triazole (phtl) (2) or 1-benzyl-4-(2,4-difluorophenyl)-1H-1,2,3-triazole (dFphtl) (3), were synthesized and isolated as their hexafluorophosphate (PF6(-)) salts and fully characterized. The single crystal structure of 3 has been solved. Along the series from 1-3 the absorption spectra shift hypsochromically while the electrochemical gap increases from 3.25 to 3.54 to 3.88 V. Acetonitrile solutions of 1 and 2 are poorly luminescent, sky-blue emitters with predominant ligand-centered and charge transfer character, respectively. Theoretical calculations support these assignments. Complex 3 is not photostable and decomposes to solvento-based structures of the form [Ir(dFphtl)2(ACN)n](+) (n = 1, 2) through a dissociation and degradation of the btl ligand.

  8. Iridium profile for 10 million years across the Cretaceous-Tertiary boundary at Gubbio (Italy) (United States)

    Alvarez, Walter; Asaro, Frank; Montanari, Alessandro


    The iridium anomaly at the Cretaceous-Tertiary (KT) boundary was discovered in the pelagic limestone sequence at Gubbio on the basis of 12 samples analyzed by neutron activation analysis (NAA) and was interpreted as indicating impact of a large extraterrestrial object at exactly the time of the KT mass extinction. Continuing controversy over the shape of the Ir profile at the Gubbio KT boundary and its interpretation called for a more detailed follow-up study. Analysis of a 57-meter-thick, 10-million-year-old part of the Gubbio sequence using improved NAA techniques revealed that there is only one Ir anomaly at the KT boundary, but this anomaly shows an intricate fine structure, the origin of which cannot yet be entirely explained. The KT Ir anomaly peaks in a 1-centimeter-thick clay layer, where the average Ir concentration is 3000 parts per trillion (ppt); this peak is flanked by tails with Ir concentrations of 20 to 80 ppt that rise above a background of 12 to 13 ppt. The fine structure of the tails is probably due in part to lateral reworking, diffusion, burrowing, and perhaps Milankovitch cyclicity.

  9. Comparison of LFM Simulated Poynting Flux With SuperDARN-Iridium Observations (United States)

    Melanson, P. D.; Murr, D.; Gagne, J.; Lyon, J.; Lotko, W.


    The solar wind interacting with the Earth's magnetosphere creates an electromagnetic connection between the ionosphere and magnetosphere through electric fields and field-aligned currents. By studying Poynting flux, we are able to better understand the energy flow in the Sun-Earth interaction. We have compared the ionospheric electric potential patterns, field-aligned current, and, for the first time, Poynting flux derived from the LFM global simulation model with observational results derived from SuperDARN and the Iridium\\texttrademark satellites. We have also examined another effect on the Poynting flux that is not normally included in global MHD simulations: self-consistent mapping of the electric field from the ionosphere to the inner simulation boundary including a field-aligned potential drop -- the so-called "Knight potential." (The effect of the Knight potential is typically only included in the proxy for the precipitating electron number and energy fluxes that enter the empirically specified ionospheric conductivity). Although the influence of the field- aligned potential drop on integrated parameters such as the transpolar potential is relatively weak, we demonstrate here that it significantly influences the global patterns of potential, field-aligned current and Poynting flux. Inclusion of the energy dissipation implied by the self-consistent electric field mapping is an important step because it more consistently represents the energy budget of the system.

  10. Characterization of secondary phosphine oxide ligands on the surface of iridium nanoparticles. (United States)

    Cano, Israel; Martínez-Prieto, Luis M; Fazzini, Pier F; Coppel, Yannick; Chaudret, Bruno; van Leeuwen, Piet W N M


    The synthesis of iridium nanoparticles (IrNPs) ligated by various secondary phosphine oxides (SPOs) is described. This highly reproducible and simple method via H2 reduction produces well dispersed, small nanoparticles (NPs), which were characterized by the state-of-the-art techniques, such as TEM, HRTEM, WAXS and ATR FT-IR spectroscopy. In particular, multinuclear solid state MAS-NMR spectroscopy with and without cross polarization (CP) enabled us to investigate the different binding modes adopted by the ligand at the nanoparticle surface, suggesting the presence of three possible types of coordination: as a purely anionic ligand Ir-P(O)R2, as a neutral acid R2P-O-H and as a monoanionic bidentate H-bonded dimer R2P-O-HO[double bond, length as m-dash]PR2. Specifically, the higher basicity of the dicyclohexyl system leads to the formation of IrNPs in which the bidentate binding mode is most abundant. Such cyclohexyl groups are bent towards the edges, as is suggested by the study of (13)CO coordination on the NP surface. This study also showed that the number of surface sites on faces available for bridging CO molecules is higher than the number of sites for terminal CO species on edges and apices, which is unexpected taking into account the small size of the nanoparticles. In addition, the IrNPs present a high chemoselectivity in the hydrogenation of cinnamaldehyde to the unsaturated alcohol.

  11. Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation (United States)

    Petra; Kamer; Spek; Schoemaker; van Leeuwen PW


    A new class of efficient catalysts was developed for the asymmetric transfer hydrogenation of unsymmetrical ketones. A series of chiral N,S-chelates (6-22) was synthesized to serve as ligands in the iridium(I)-catalyzed reduction of ketones. Both formic acid and 2-propanol proved to be suitable as hydrogen donors. Sulfoxidation of an (R)-cysteine-based aminosulfide provided a diastereomeric ligand family containing a chiral sulfur atom. The two chiral centers of these ligands showed a clear effect of chiral cooperativity. In addition, aminosulfides containing two asymmetric carbon atoms in the backbone were synthesized. Both the sulfoxide-containing beta-amino alcohols and the aminosulfides derived from 1,2-disubstituted amino alcohols gave rise to high reaction rates and moderate to excellent enantioselectivities in the reduction of various ketones. The enantioselective outcome of the reaction was favorably affected by selecting the most appropriate hydrogen donor. Enantioselectivities of up to 97% were reached in the reduction of aryl-alkyl ketones.

  12. High-level ab initio computations of the absorption spectra of organic iridium complexes. (United States)

    Plasser, Felix; Dreuw, Andreas


    The excited states of fac-tris(phenylpyridinato)iridium [Ir(ppy)3] and the smaller model complex Ir(C3H4N)3 are computed using a number of high-level ab initio methods, including the recently implemented algebraic diagrammatic construction method to third-order ADC(3). A detailed description of the states is provided through advanced analysis methods, which allow a quantification of different charge transfer and orbital relaxation effects and give extended insight into the many-body wave functions. Compared to the ADC(3) benchmark an unexpected striking difference of ADC(2) is found for Ir(C3H4N)3, which derives from an overstabilization of charge transfer effects. Time-dependent density functional theory (TDDFT) using the B3LYP functional shows an analogous but less severe error for charge transfer states, whereas the ωB97 results are in good agreement with ADC(3). Multireference configuration interaction computations, which are in reasonable agreement with ADC(3), reveal that static correlation does not play a significant role. In the case of the larger Ir(ppy)3 complex, results at the TDDFT/B3LYP and TDDFT/ωB97 levels of theory are presented. Strong discrepancies between the two functionals, which are found with respect to the energies, characters, as well as the density of the low lying states, are discussed in detail and compared to experiment.

  13. Iridium, platinum and rhodium baseline concentration in lichens from Tierra del Fuego (South Patagonia, Argentina). (United States)

    Pino, Anna; Alimonti, Alessandro; Conti, Marcelo Enrique; Bocca, Beatrice


    Lichen samples of Usnea barbata were used as possible biomonitors of the atmospheric background level of iridium (Ir), platinum (Pt) and rhodium (Rh) in the remote region of Tierra del Fuego (South Patagonia, Argentina). Lichens were collected in 2006 at 53 sites covering 7 different areas of the region (24 transplanted lichens of the northern region and 29 native lichen samples of the central-southern region). A microwave acidic digestion procedure was used to mineralize the samples and a sector field inductively coupled plasma mass spectrometry method was developed to quantify the elements. The study of the influence of interferences on analyte signals and a quality control procedure were carried out. The analytical protocol was further applied to evaluate Ir, Pt and Rh bioaccumulation in lichens. The detection limits obtained were 0.010 ng g⁻¹, 0.013 ng g⁻¹ and 0.030 ng g⁻¹ for Ir, Pt and Rh, respectively. Recoveries at different fortification levels were between 96.3% and 106% and precision was 3.3% on average. The metals concentration (as dry weight) spanned the following ranges: Ir, Tierra del Fuego. Values detected are more likely influenced by the long-range atmospheric transport of these pollutants and, in comparison with densely populated areas in the world, they can represent the baseline for low impacted areas.

  14. Selective molecular recognition by nanoscale environments in a supported iridium cluster catalyst (United States)

    Okrut, Alexander; Runnebaum, Ron C.; Ouyang, Xiaoying; Lu, Jing; Aydin, Ceren; Hwang, Son-Jong; Zhang, Shengjie; Olatunji-Ojo, Olayinka A.; Durkin, Kathleen A.; Dixon, David A.; Gates, Bruce C.; Katz, Alexander


    The active sites of enzymes are contained within nanoscale environments that exhibit exquisite levels of specificity to particular molecules. The development of such nanoscale environments on synthetic surfaces, which would be capable of discriminating between molecules that would nominally bind in a similar way to the surface, could be of use in nanosensing, selective catalysis and gas separation. However, mimicking such subtle behaviour, even crudely, with a synthetic system remains a significant challenge. Here, we show that the reactive sites on the surface of a tetrairidium cluster can be controlled by using three calixarene-phosphine ligands to create a selective nanoscale environment at the metal surface. Each ligand is 1.4 nm in length and envelopes the cluster core in a manner that discriminates between the reactivities of the basal-plane and apical iridium atoms. CO ligands are initially present on the clusters and can be selectively removed from the basal-plane sites by thermal dissociation and from the apical sites by reactive decarbonylation with the bulky reactant trimethylamine-N-oxide. Both steps lead to the creation of metal sites that can bind CO molecules, but only the reactive decarbonylation step creates vacancies that are also able to bond to ethylene, and catalyse its hydrogenation.

  15. Reducing HAuCl{sub 4} by the C{sub 60} dianion: C{sub 60}-directed self-assembly of gold nanoparticles into novel fullerene bound gold nanoassemblies

    Energy Technology Data Exchange (ETDEWEB)

    Liu Wei; Gao Xiang [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Graduate School of the Chinese Academy of Sciences, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022 (China)], E-mail:


    The C{sub 60} dianion is used to reduce tetrachloroauric acid (HAuCl{sub 4}) for the first time; three-dimensional C{sub 60} bound gold (Au-C{sub 60}) nanoclusters are obtained from C{sub 60}-directed self-assembly of gold nanoparticles due to the strong affinities of Au-C{sub 60} and C{sub 60}-C{sub 60}. The process was monitored in situ by UV-vis-NIR spectroscopy. The resulting Au-C{sub 60} nanoclusters were characterized using transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy-dispersive spectroscopy (EDS), x-ray powder diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and FT-IR and Raman spectroscopies. TEM demonstrates the formation of 3D nanonetwork aggregates, which are composed of discrete gold nanocores covered with a C{sub 60} monolayer. The SAED and XRD patterns indicate that the gold nanocores inside the capped C{sub 60} molecules belong to the face-centred cubic crystal structure, while the C{sub 60} molecules are amorphous. The EDS and XPS measurements validate that the Au-C{sub 60} nanoclusters contain only Au and C elements and Au{sup 3+} is reduced to Au{sup 0}. FT-IR spectroscopy shows the chemiadsorption of C{sub 60} to the gold nanocores, while Raman spectroscopy demonstrates the electron transfer from the gold nanocores to the chemiadsorbed C{sub 60} molecules. Au-C{sub 60} nanoclusters embedded in tetraoctyl-n-ammonium bromide (TOAB) on glassy carbon electrodes (GCEs) have been fabricated and have shown stable and well-defined electrochemical responses in aqueous solution.

  16. Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Songchen [Ames Laboratory; Manna, Kuntal [Ames Laboratory; Ellern, Arkady [Ames Laboratory; Sadow, Aaron D [Ames Laboratory


    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(η4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(η4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(η4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(η4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(μ-Cl)(η2-C8H14)2]2 (M = Rh, Ir) provide {κ4-PhB(OxMe2)2ImMes'CH2}Rh(μ-H)(μ-Cl)Rh(η2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(η3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in C–H bond oxidative addition providing the compounds {κ4-PhB(OxMe2)2ImMes'CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis

  17. On the concept of hemilability: insights into a donor-functionalized iridium(I) NHC motif and its impact on reactivity. (United States)

    Riener, Korbinian; Bitzer, Mario J; Pöthig, Alexander; Raba, Andreas; Cokoja, Mirza; Herrmann, Wolfgang A; Kühn, Fritz E


    Novel iridium(I) complexes bearing N-donor-functionalized N-heterocyclic carbene ligands were synthesized. Although hemilabile coordination of the attached donor is considered beneficial in catalysis, no detailed study of this phenomenon in these systems is available to date. The present report provides insight into the hemilabile bonding properties of a N,N'-bis(pyridin-2-yl)-imidazolylidene (NCN) ligand motif on iridium(I). In most cases, the presented compounds exhibit rare fluxional hemilabile coordination of the N donor, and remarkable performance in catalytic transfer hydrogenation is observed. Further, extensive reactivity studies often led to unexpected products.

  18. Hybrid white organic light-emitting devices based on phosphorescent iridium-benzotriazole orange-red and fluorescent blue emitters

    Energy Technology Data Exchange (ETDEWEB)

    Xia, Zhen-Yuan, E-mail: [Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, Shanghai 200237 (China); Su, Jian-Hua [Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, Shanghai 200237 (China); Chang, Chi-Sheng; Chen, Chin H. [Display Institute, Microelectronics and Information Systems Research Center, National Chiao Tung University, Hsinchu, Taiwan 300 (China)


    We demonstrate that high color purity or efficiency hybrid white organic light-emitting devices (OLEDs) can be generated by integrating a phosphorescent orange-red emitter, bis[4-(2H-benzotriazol-2-yl)-N,N-diphenyl-aniline-N{sup 1},C{sup 3}] iridium acetylacetonate, Ir(TBT){sub 2}(acac) with fluorescent blue emitters in two different emissive layers. The device based on deep blue fluorescent material diphenyl-[4-(2-[1,1 Prime ;4 Prime ,1 Double-Prime ]terphenyl-4-yl-vinyl)-phenyl]-amine BpSAB and Ir(TBT){sub 2}(acac) shows pure white color with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.33,0.30). When using sky-blue fluorescent dopant N,N Prime -(4,4 Prime -(1E,1 Prime E)-2,2 Prime -(1,4-phenylene)bis(ethene-2,1-diyl) bis(4,1-phenylene))bis(2-ethyl-6-methyl-N-phenylaniline) (BUBD-1) and orange-red phosphor with a color-tuning phosphorescent material fac-tris(2-phenylpyridine) iridium (Ir(ppy){sub 3} ), it exhibits peak luminance yield and power efficiency of 17.4 cd/A and 10.7 lm/W, respectively with yellow-white color and CIE color rendering index (CRI) value of 73. - Highlights: Black-Right-Pointing-Pointer An iridium-based orange-red phosphor Ir(TBT){sub 2}(acac) was applied in hybrid white OLEDs. Black-Right-Pointing-Pointer Duel- and tri-emitter WOLEDs were achieved with either high color purity or efficiency performance. Black-Right-Pointing-Pointer Peak luminance yield of tri-emitter WOLEDs was 17.4 cd/A with yellow-white color and color rendering index (CRI) value of 73.

  19. Highly efficient electrophosphorescence devices based on iridium complexes with high efficiency over a wide range of current densities

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Liying; Li Bin; Hong Ziruo [Key Laboratory of Excited State Processes, Changchun Institute of Optics, Fine Mechanics and Physics, Changchun 130033 (China); Chen Ping; Liu Shiyong [State Key Lab of Integrated Optoelectronics, Jilin University, Changchun 130023 (China)], E-mail:, E-mail:


    Three new luminescent cyclometalated iridium (II I) complexes are successfully synthesized. The cyclometalated ligand used here is 2-(2-fluorophenyl)-benzothiazole (F-BT). The auxiliary ligands are acetylacetone (acac), 1,1,1-trifluoroacetylaceton (3F-acac), 1,1,1,5,5,5-hexafluoroacetylacetone (6F-acac), respectively. All complexes exhibit bright photoluminescence at room temperature. Organic light-emitting diodes are fabricated by doping the iridium (III) complexes in 4, 4' -N, N'-dicarbazole-biphenyl (CBP), and the device characteristics are investigated. Among these devices, the performances of the optimized devices based on 1 at high current density are among the best reported for devices with iridium (III) complexes as emitters. EL efficiencies show weak dependence on doping concentration and current density. The optimized device exhibits a peak current efficiency of 28.5 cd A{sup -1} and a power efficiency of 11.2 lm W{sup -1}, respectively, at 20 mA cm{sup -2}, an efficiency of 22.7 cd A{sup -1} at 100 mA cm{sup -2}, 80% of the maximum, can be achieved. Short triplet decay time of 1 measured in solid films is supposed to be responsible for the minor loss in EL efficiency, which suggests depressed triplet-triplet annihilation and site saturation of the phosphor. Efficient exciton formation on the molecules of 1 by direct charge trapping and confinement within the emissive layer also make for outstanding electrophosphorescent performances.

  20. Preparation of iridium nano-and submicroparticles on solid substrates by direct surface growth and drop-drying assembly

    Institute of Scientific and Technical Information of China (English)


    Iridium nanoparticles (IrNPs) and submicroparticles (IrSMPs) with different shapes were synthesized and assembled on indium thin oxide (ITO) and Si substrates using two different methods: direct surface growth and drop-drying assembly. The obtained IrNPs and IrSMPs were characterized using scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The IrSMPs (or IrNPs) with disc-like shape and irregular shapes were obtained on ITO substrate by direct surface growth method using polyvinylpy...

  1. Study of macro- and micro-segregation of iridium in molybdenum single crystals after electron beam zone melting

    Energy Technology Data Exchange (ETDEWEB)

    Drapala, Jaromir; Skotnicova, Katerina [VSB-Technical University of Ostrava (Czech Republic). Dept. of Non-ferrous Metals, Refining and Recycling


    The aim of the work was to study the creation of micro- and macro-segregation of iridium in low-alloyed molybdenum single crystals after electron beam zone melting (floating zone technique) depending on various conditions of crystallization. In order to evaluate relations between the chemical inhomogeneity and structural defects and their influence on properties of single crystals, the dependence of concentration and character of distribution of admixtures under various crystallization conditions on the origin of concentration undercooling and dislocation substructure of molybdenum single crystals prepared by electron beam floating zone melting was experimentally investigated.

  2. Direct, intermolecular, enantioselective, iridium-catalyzed allylation of carbamates to form carbamate-protected, branched allylic amines. (United States)

    Weix, Daniel J; Marković, Dean; Ueda, Mitsuhiro; Hartwig, John F


    The direct reaction between carbamates and achiral allylic carbonates to form branched, conveniently protected primary allylic amines with high regioselectivity and enantioselectivity is reported. This process occurs without base or with 0.5 equiv K(3)PO(4) in the presence of a metalacyclic iridium catalyst containing a labile ethylene ligand. The reactions of aryl-, heteroaryl-, and alkyl-substituted allylic carbonates with BocNH(2), FmocNH(2), CbzNH(2), TrocNH(2), TeocNH(2), and 2-oxazolidinone occur in good yields, with high selectivity for the branched isomer and high enantioselectivities (98% average ee).

  3. Synthesis, characterization, and photophysical and electroluminescent properties of blue-emitting cationic iridium(III) complexes bearing nonconjugated ligands. (United States)

    Zhang, Fuli; Ma, Dongxin; Duan, Lian; Qiao, Juan; Dong, Guifang; Wang, Liduo; Qiu, Yong


    The development of pure-blue-to-deep-blue-emitting ionic phosphors is an ultimate challenge for full-color displays and white-light sources. Herein we report two series of short-wavelength light-emitting cationic iridium(III) complexes with nonconjugated ancillary and cyclometalating ligands, respectively. In the first series, nonconjugated 1-[(diphenylphosphino)methyl]-3-methylimidazolin-2-ylidene-C,C2' (dppmmi) is used as the ancillary ligand and 2-phenylpyridine (ppy), 2-(2,4-difluorophenyl)pyridine (dfppy), and 1-(2,4-difluorophenyl)-1H-pyrazole (dfppz) are used as cyclometalating ligands. In the second one, nonconjugated 2,4-difluorobenzyl-N-pyrazole (dfbpz) is used as the cyclometalating ligand and 3-methyl-1-(2-pyridyl)benzimidazolin-2-ylidene-C,C(2)' (pymbi) as the ancillary ligand. The synthesis and photophysical and electrochemical properties, together with the X-ray crystal structures of these complexes, have been investigated. At room temperature, blue-emitting complexes [Ir(ppy)2(dppmmi)]PF6 (1) and [Ir(dfppy)2(dppmmi)]PF6 (2; PF6(-) is hexafluorophosphate) show much larger photoluminescence quantum yields of 24% and 46%, respectively. On the contrary, for complexes [Ir(dfppz)2(dppmmi)]PF6 (3) and [Ir(dfbpz)2(pymbi)]PF6 (4), deep-blue luminescence is only observed at low temperature (77 K). Density functional theory calculations are used to rationalize the differences in the photophysical behavior observed upon changes of the ligands. It is shown that the electronic transition dipoles of cationic iridium complexes 1 and 2 are mainly confined to cyclometalated ligands ((3)MLCT and LC (3)π-π*) and those of complex 3 are confined to all of the ligands ((3)MLCT, LC (3)π-π*, and (3)LLCT) because of the high LUMO energy level of dfppz. The emission of 4 mainly originates from the central iridium(III) ion and cyclometalated ligand to ancillary ligand charge transfer ((3)MLCT and (3)LLCT), in contrast to commonly designed cationic complexes using carbene

  4. Substrate arrays of iridium oxide microelectrodes for in vitro neuronal interfacing

    Directory of Open Access Journals (Sweden)

    Shady Gawad


    Full Text Available The design of novel bidirectional interfaces for in vivo and in vitro nervous systems is an important step towards future functional neuroprosthetics. Small electrodes, structures and devices are necessary to achieve high-resolution and target-selectivity during stimulation and recording of neuronal networks, while significant charge transfer and large signal-to-noise ratio are required for accurate time resolution. In addition, the physical properties of the interface should remain stable across time, especially when chronic in vivo applications or in vitro long-term studies are considered, unless a procedure to actively compensate for degradation is provided. In this short report, we describe the use and fabrication of arrays of 120 planar microelectrodes (MEAs of sputtered Iridium Oxide (IrOx. The effective surface area of individual microelectrodes is significantly increased using electrochemical activation, a procedure that may also be employed to restore the properties of the electrodes as required. The electrode activation results in a very low interface impedance, especially in the lower frequency domain, which was characterized by impedance spectroscopy. The increase in the roughness of the microelectrodes surface was imaged using digital holographic microscopy and electron microscopy. Aging of the activated electrodes was also investigated, comparing storage in saline with storage in air. Demonstration of concept was achieved by recording multiple single-unit spike activity in acute brain slice preparations of rat neocortex. Data suggests that extracellular recording of action potentials can be achieved with planar IrOx MEAs with good signal-to-noise ratios.

  5. Iridium oxide microelectrode arrays for in vitro stimulation of individual rat neurons from dissociated cultures. (United States)

    Eick, Stefan; Wallys, Jens; Hofmann, Boris; van Ooyen, André; Schnakenberg, Uwe; Ingebrandt, Sven; Offenhäusser, Andreas


    We present the first in vitro extracellular stimulation of individual neurons from dissociated cultures with iridium oxide (IrO(x)) electrodes. Microelectrode arrays with sputtered IrO(x) films (SIROF) were developed for electrophysiological investigations with electrogenic cells. The microelectrodes were characterized with scanning electron and atomic force microscopy, revealing rough and porous electrodes with enlarged surface areas. As shown by cyclic voltammetry and electrochemical impedance spectroscopy, the large surface area in combination with the good electrochemical properties of SIROF resulted in high charge storage capacity and low electrode impedance. Thus, we could transfer the good properties of IrO(x) as material for in vivo stimulation electrodes to multi-electrode arrays with electrode diameters as small as 10 mum for in vitro applications. Single rat cortical neurons from dissociated cultures were successfully stimulated to fire action potentials using single or trains of biphasic rectangular voltage-controlled stimulation pulses. The stimulated cell's membrane potential was simultaneously monitored using whole-cell current-clamp recordings. This experimental configuration allowed direct evaluation of the influence of pulse phase sequence, amplitude, and number on the stimulation success ratio and action potential latency. Negative phase first pulses were more effective for extracellular stimulation and caused reduced latency in comparison to positive phase first pulses. Increasing the pulse amplitude also improved stimulation reliability. However, in order to prevent cell or electrode damage, the pulse amplitude is limited to voltages below the threshold for irreversible electrochemical reactions at the electrode. As an alternative to increasing the amplitude, a higher number of stimulation pulses was also shown to increase stimulation success.

  6. Iridium oxide microelectrode arrays for in vitro stimulation of individual rat neurons from dissociated cultures

    Directory of Open Access Journals (Sweden)

    Stefan Eick


    Full Text Available We present the first in-vitro extracellular stimulation of individual neurons from dissociated cultures with iridium oxide (IrOx electrodes. Microelectrode arrays with sputtered IrOx films (SIROF were developed for electrophysiological investigations with electrogenic cells. The microelectrodes were characterized with scanning electron and atomic force microscopy, revealing rough and porous electrodes with enlarged surface areas. As shown by cyclic voltammetry and electrochemical impedance spectroscopy, the large surface area in combination with the good electrochemical properties of SIROF resulted in high charge storage capacity and low electrode impedance. Thus, we could transfer the good properties of IrOx as material for in-vivo stimulation electrodes to MEAs with electrode diameters as small as 10 µm for in-vitro applications. Single rat cortical neurons from dissociated cultures were successfully stimulated to fire action potentials using single or trains of biphasic rectangular voltage-controlled stimulation pulses. The stimulated cell’s membrane potential was simultaneously monitored using whole-cell current-clamp recordings. This experimental configuration allowed direct evaluation of the influence of pulse phase sequence, amplitude, and number on the stimulation success ratio and action potential latency. Negative phase first pulses were more effective for extracellular stimulation and caused reduced latency in comparison to positive phase first pulses. Increasing the pulse amplitude also improved stimulation reliability. However, in order to prevent cell or electrode damage, the pulse amplitude is limited to voltages below the threshold for irreversible electrochemical reactions at the electrode. As an alternative to increasing the amplitude, a higher number of stimulation pulses was also shown to increase stimulation success.

  7. Anodic deposition of colloidal iridium oxide thin films from hexahydroxyiridate(IV) solutions. (United States)

    Zhao, Yixin; Vargas-Barbosa, Nella M; Hernandez-Pagan, Emil A; Mallouk, Thomas E


    A facile, in-situ deposition route to stable iridium oxide (IrO(x)·nH(2)O) nanoparticle thin films from [Ir(OH)(6)](2-) solutions is reported. The [Ir(OH)(6)](2-) solution, made by alkaline hydrolysis of [IrCl(6)](2-), is colorless and stable near neutral pH, and forms blue IrO(x)·nH(2)O nanoparticle suspensions once it is adjusted to acidic or basic conditions. IrO(x)·nH(2)O nanoparticle thin films are grown anodically on glassy carbon, fluorine-doped tin oxide, and gold electrodes by electrolyzing [Ir(OH)(6)](2-) solutions at +1.0-1.3 V versus Ag/AgCl. The thickness of the IrO(x)·nH(2)O films can be controlled by varying the concentration of [Ir(OH)(6)](2-) , the deposition potential, and/or the deposition time. These thin films are stable between pH 1 and 13 and have the lowest overpotential (η) for the oxygen evolution reaction (OER) of any yet reported. Near neutral pH, the Tafel slope for the OER at a IrO(x)·nH(2)O film/Au rotating disk electrode was 37-39 mV per decade. The exchange current density for the OER was 4-8 × 10(-10) A cm(-2) at a 4 mC cm(-2) coverage of electroactive Ir.

  8. Highly effective water oxidation catalysis with iridium complexes through the use of NaIO4. (United States)

    Codolà, Zoel; Cardoso, João M S; Royo, Beatriz; Costas, Miquel; Lloret-Fillol, Julio


    Exceptional water oxidation (WO) turnover frequencies (TOF=17,000 h(-1)), and turnover numbers (TONs) close to 400,000, the largest ever reported for a metal-catalyzed WO reaction, have been found by using [Cp*Ir(III)(NHC)Cl2] (in which NHC=3-methyl-1-(1-phenylethyl)-imidazoline-2-ylidene) as the pre-catalyst and NaIO4 as oxidant in water at 40 °C. The apparent TOF for [Cp*Ir(III)(NHC)X2] (1X, in which X stands for I (1I), Cl (1Cl), or triflate anion (1OTf)) and [(Cp*-NHCMe)Ir(III)I2] (2) complexes, is kept constant during almost all of the O2 evolution reaction when using NaIO4 as oxidant. The TOF was found to be dependent on the ligand and on the anion (TOF ranging from ≈600 to ≈1100 h(-1) at 25 °C). Degradation of the complexes by oxidation of the organic ligands upon reaction with NaIO4 has been investigated. (1)H NMR, ESI-MS, and dynamic light-scattering measurements (DLS) of the reaction medium indicated that the complex undergoes rapid degradation, even at low equivalents of oxidant, but this process takes place without formation of nanoparticles. Remarkably, three-month-old solution samples of oxidized pre-catalysts remain equally as active as freshly prepared solutions. A UV/Vis feature band at λmax =405 nm is observed in catalytic reaction solutions only when O2 evolves, which may be attributed to a resting state iridium speciation, most probably Ir-oxo species with an oxidation state higher than IV.

  9. On the mechanism of the dehydroaromatization of hexane to benzene by an iridium pincer catalyst. (United States)

    Thawani, Akanksha; Rajeev, Ramanan; Sunoj, Raghavan B


    The developments in the area of transition-metal pincer complexes have opened up new avenues for conversion of saturated hydrocarbons to more useful aromatic compounds under homogeneous reaction conditions. In the backdrop of an interesting series of conversions of unbranched alkanes to benzene, toluene, and xylene (known as the BTX family aromatics) reported by Goldman and co-workers (Nature Chem. 2011, 3, 167), we herein present a comprehensive mechanistic picture obtained by using density functional computations. The reaction involves an iridium-PCP-pincer-catalyzed dehydroaromatization of hexane to benzene (in which PCP=η(3) -C6 H3 (iPrP)2 -1,3) by using tert-butylethylene (TBE) as a sacrificial acceptor. The most energetically preferred pathway for a sequence of dehydrogenations is identified to begin with a terminal CH bond activation of n-hexane leading to the formation of hex-1-ene. Although the initial dehydrogenation of n-hexane was found to be endergonic, the accompanying exoergic hydrogenation of TBE to tert-butylethane (TBA) compensates the energetics to keep the catalytic cycle efficient. Subsequent dehydrogenations provide a hexa-1,3-diene and then a hexa-1,3,5-triene. The pincer bound triene is identified to undergo cyclization to furnish cyclohexadiene. Eventually, dehydrogenation of cyclohexa-1,3-diene offers benzene. In the most preferred pathway, the Gibbs free energy barrier for cyclization leading to the formation of cyclohexa-1,3-diene is found to exhibit the highest barrier (21.7 kcal mol(-1) ).

  10. Theoretical characterization and design of highly efficient iridium (III) complexes bearing guanidinate ancillary ligand. (United States)

    Ren, Xin-Yao; Wu, Yong; Wang, Li; Zhao, Liang; Zhang, Min; Geng, Yun; Su, Zhong-Min


    A density functional theory/time-depended density functional theory was used to investigate the synthesized guanidinate-based iridium(III) complex [(ppy)2Ir{(N(i)Pr)2C(NPh2)}] (1) and two designed derivatives (2 and 3) to determine the influences of different cyclometalated ligands on photophysical properties. Except the conventional discussions on geometric relaxations, absorption and emission properties, many relevant parameters, including spin-orbital coupling (SOC) matrix elements, zero-field-splitting parameters, radiative rate constants (kr) and so on were quantitatively evaluated. The results reveal that the replacement of the pyridine ring in the 2-phenylpyridine ligand with different diazole rings cannot only enlarge the frontier molecular orbital energy gaps, resulting in a blue-shift of the absorption spectra for 2 and 3, but also enhance the absorption intensity of 3 in the lower-energy region. Furthermore, it is intriguing to note that the photoluminescence quantum efficiency (ΦPL) of 3 is significantly higher than that of 1. This can be explained by its large SOC value(n=3-4) and large transition electric dipole moment (μS3), which could significantly contribute to a larger kr. Besides, compared with 1, the higher emitting energy (ET1) and smaller (2) value for 3 may lead to a smaller non-radiative decay rate. Additionally, the detailed results also indicate that compared to 1 with pyridine ring, 3 with imidazole ring performs a better hole injection ability. Therefore, the designed complex 3 can be expected as a promising candidate for highly efficient guanidinate-based phosphorescence emitter for OLEDs applications. Copyright © 2014 Elsevier Inc. All rights reserved.

  11. Defective Metal-Organic Frameworks Incorporating Iridium-Based Metalloligands: Sorption and Dye Degradation Properties. (United States)

    Fan, Kun; Nie, Wei-Xuan; Wang, Lu-Ping; Liao, Chwen-Haw; Bao, Song-Song; Zheng, Li-Min


    Artificial control and engineering of metal-organic framework (MOF) crystals with defects can endow them with suitable properties for applications in gas storage, separation, and catalysis. A series of defective iridium-containing MOFs, [Zn4 (μ4 -O)(Ir-A)2(1-x) (Ir-B)2x ] (ZnIr-MOF-dx ), were synthesized by doping heterostructured linker Ir-BH3 into the parent [Zn4 (μ4 -O)(Ir-A)2 ] (ZnIr-MOF), in which Ir-AH3 represents [Ir(ppy-COOH)3 ] (ppyCOOH=3-(pyridin-2-yl)benzoic acid) and Ir-BH3 is [Ir(ppy-COOH)2 (2-pyPO3 H)] (2-pyPO3 H2 =2-pyridylphosphonic acid). Samples with different degrees of defects were characterized by SEM, IR and NMR spectroscopy, powder XRD measurements, and thermal and elemental analyses. ZnIr-MOF-d0.3 was selected as a representative for gas (N2 , CO2 ) or vapor (H2 O, alcohol) sorption studies. The results demonstrate that defective ZnIr-MOF-d0.3 possesses multiple pore size distributions, ranging from micro- to mesopores, unlike the parent material, which shows a uniform micropore distribution. The hydrophilicity of the interior surface is also increased after defect engineering. As a result, ZnIr-MOF-d0.3 shows an enhanced adsorption capability toward n-butanol, relative to that of the parent compound. Optical studies reveal that both ZnIr-MOF and ZnIr-MOF-d0.3 have low band gaps (2.35 and 2.40 eV), corresponding to semiconductors. ZnIr-MOF-d0.3 exhibits dramatically increased photocatalytic efficiency for dye degradation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Iridium as permanent modifier in the determination of lead in whole blood and urine by electrothermal atomic absorption spectrometry (United States)

    Grinberg, Patricia; de Campos, Reinaldo Calixto


    The behavior of Iridium as a thermally deposited permanent modifier for the determination of lead by GFAAS was studied. The iridium coating procedure was optimized using a two-level factorial design. Using the optimized coating procedure, up to 1100 firings were possible with the same coating without sensitivity losses. The system was used in the determination of lead in whole blood and urine. A mixture of 0.1% Triton X-100 and 0.2% nitric acid was used as diluent. Pyrolysis temperature was 800°C for both matrices. Spiked, low-level samples were used for calibration. Under these conditions, no significant difference was found in comparison to the results obtained using a validated conventional modification procedure employing phosphate as modifier. Also, good agreement between found and certified/reference values were observed in the analysis of certified and commercial quality control materials, respectively. Such agreement was observed even using a 1100 times fired Ir coated platform-graphite tube assembly.

  13. Dosimetry of wires and single ribbons of Iridium 192; Dosimetria de alambres y ribbons individuales de Iridio-192

    Energy Technology Data Exchange (ETDEWEB)

    Mazzucco, L.D. [Centro Medico Nuclear S.R.L. San Juan (Argentina)


    The objective of this work is in order to present in table formats the dosimetry of wires and single ribbons of Iridium with lengths 1-12 cm for each one linear source along the bisector which is perpendicular at tissue sources (water) computed for linear activity 1 mCi/cm in the case of wires, and 1 mCi/seed for ribbons. The above tables are of direct use, adaptable at particular cases so they facilitate logarithmic graphics of doses in function of the distance for interpolation and use in the treatments planning. It was shown that for two sources with identical linear activity and total length, one of the equidistant seeds at 1 cm (ribbon) and one wire on the other hand, the differences in dose rates in near positions can be about the 15% so corroborating that it is not possible to use wire tables for seeds neither vice versa. Moreover it was elaborated tables of practical direct use for dose rate in water at c Gy/hr for wires and Ribbons 1-12 cm length and from 0.5-10 cm of distance in the perpendicular bisector at the Iridium implant. (Author)

  14. Silica nanoparticles for micro-particle imaging velocimetry: fluorosurfactant improves nanoparticle stability and brightness of immobilized iridium(III) complexes. (United States)

    Lewis, David J; Dore, Valentina; Rogers, Nicola J; Mole, Thomas K; Nash, Gerard B; Angeli, Panagiota; Pikramenou, Zoe


    To establish highly luminescent nanoparticles for monitoring fluid flows, we examined the preparation of silica nanoparticles based on immobilization of a cyclometalated iridium(III) complex and an examination of the photophysical studies provided a good insight into the Ir(III) microenvironment in order to reveal the most suitable silica nanoparticles for micro particle imaging velocimetry (μ-PIV) studies. Iridium complexes covalently incorporated at the surface of preformed silica nanoparticles, [Ir-4]@Si500-Z, using a fluorinated polymer during their preparation, demonstrated better stability than those without the polymer, [Ir-4]@Si500, as well as an increase in steady state photoluminescence intensity (and therefore particle brightness) and lifetimes which are increased by 7-fold compared with nanoparticles with the same metal complex attached covalently throughout their core, [Ir-4]⊂Si500. Screening of the nanoparticles in fluid flows using epi-luminescence microscopy also confirm that the brightest, and therefore most suitable particles for microparticle imaging velocimetry (μ-PIV) measurements are those with the Ir(III) complex immobilized at the surface with fluorosurfactant, that is [Ir-4]@Si500-Z. μ-PIV studies demonstrate the suitability of these nanoparticles as nanotracers in microchannels.

  15. An iridium-mediated C-H activation/CO2-carboxylation reaction of 1,1-bisdiphenylphosphinomethane. (United States)

    Langer, Jens; Fabra, María José; García-Orduña, Pilar; Lahoz, Fernando J; Görls, Helmar; Oro, Luis A; Westerhausen, Matthias


    The reaction of 1,1-bisdiphenylphosphinomethane (dppm, 4 eq.) with [IrCl(coe)(2)](2) results in a solvent dependent equilibrium from which the complexes [IrCl(dppm)(dppm-H)(H)] (1) and [Ir(dppm)(2)]Cl (2) were isolated. When 2 is dissolved in methanol, [IrCl(dppm)(2)(H)][OCH(3)] (4) is formed as dominant species in solution. The C-H activation reaction which leads to 1 and 4 can be suppressed by adding an additional dppm ligand per iridium center resulting in the formation of [Ir(dppm)(3)]Cl (5). If the reaction of dppm with [IrX(coe)(2)](2) (X = Cl, I) is performed under an atmosphere of CO(2) the complexes [IrX(dppm)(H){(Ph(2)P)(2)C-COOH}] (6: X = Cl; 7: X = I) are formed by a CH activation/CO(2) carboxylation sequence. The reaction of 6 with NH(4)PF yields [IrCl(dppm)(2)(H)]PF(6).(10). Additionally the lithium compounds [Li(dme)(2)(dppm-H)] (3) and [Li(dme){(Ph(2)P)(2)CHCOO}](2) (8) were prepared for comparison. The molecular structures of the compounds 1, 3, 5, 7, 8 and of the related iridium complex [IrCl(dppm)(2)(H)]I (11) are reported.

  16. Phosphorescent Chemosensor Based on Iridium(III) Complex for the Selective Detection of Cu(II) Ion in Aqueous Acetonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hyebin; Li, Yinan; Hyun, Myungho [Pusan National Univ., Busan (Korea, Republic of)


    Iridium(III) complex 1 containing two cyclo-metalating 2-phenylpyridine (ppy) ligands and one 2,2'-bipyridine ligand tethered with two DPA moieties by a methylene linker was prepared. Iridium(III) complex 1 was found to form 1:2 complex selectively with Cu(II) ion with the Stern-Volmer constant of 5.8 Χ 10{sup 4} M{sup -1}. Cu(II) ion has two sides. In one side, Cu(II) ion is an important cofactor in nearly 20 metalloenzymes and an essential micronutrient for all living systems. But, in other side, Cu(II) ion is one of significant metal pollutants and toxic to living cells if present in slightly high concentrations, causing neurodegenerative diseases such as Menkes and Wilson's disease. In this instance, the selective detection of Cu(II) ion in environment and in living systems is very important. Consequently, various fluorescent chemosensors for the highly sensitive and selective detection of Cu (II) ion have been developed.

  17. Probing the mer- to fac-isomerization of tris-cyclometallated homo- and heteroleptic (C,N)3 Iridium(III) complexes

    NARCIS (Netherlands)

    McDonald, A.R.; Lutz, M.; von Chrzanowski, L.S.; van Klink, G.P.M.; Spek, A.L.; van Koten, G.


    We have developed techniques which allow for covalent tethering, via a “hetero” cyclometallating ligand, of heteroleptic tris-cyclometallated iridium(III) complexes to polymeric supports (for application in light-emitting diode technologies). This involved the selective synthesis and thorough charac

  18. Application of cellulose anion-exchangers to separation of palladium from platinum or iridium with glycine as complexing agent and atomic-absorption spectrometry for detection. (United States)

    Brajter, K; Słonawska, K


    The use of glycine as complexing agent for chromatographie separation of palladium from platinum, or palladium from iridium, on cellulose anion-exchangers has been investigated and found possible over a wide range of concentration ratios. The method can be used for analysis of Pd-Ir alloys. The nature of the complexes taking part in the ion-exchange has been identified.

  19. Reactions of the dianion [1,1,1-(CO)3-2-Ph-closo-1,2-MnCB9H9]2- with transition-metal cations: facile insertion and then extrusion of cluster vertexes. (United States)

    Du, Shaowu; Jeffery, John C; Kautz, Jason A; Lu, Xiu Lian; McGrath, Thomas D; Miller, Thomas A; Riis-Johannessen, T; Stone, F Gordon A


    The manganacarborane dianion in [N(PPh(3))(2)][NEt(4)][1,1,1-(CO)(3)-2-Ph-closo-1,2-MnCB(9)H(9)] (1b) reacts with cationic transition metal-ligand fragments to give products in which the electrophilic metal groups (M') are exo-polyhedrally attached to the {closo-1,2-MnCB(9)} cage system via three-center two-electron B-H --> M' linkages and generally also by Mn-M' bonds. With {Cu(PPh(3))}(+), the Cu-Mn-Cu trimetallic species [1,6-{Cu(PPh(3))}-1,7-{Cu(PPh(3))}-6,7-(mu-H)(2)-1,1,1-(CO)(3)-2-Ph-closo-1,2-MnCB(9)H(7)] (3a) is formed, whereas reactions with {M'(dppe)}(2+) (M' = Ni, Pd; dppe = Ph(2)PCH(2)CH(2)PPh(2)) give [1,3-{Ni(dppe)}-3-(mu-H)-1,1,1-(CO)(3)-2-Ph-closo-1,2-MnCB(9)H(8)] (5a) and [1,3,6-{Pd(dppe)}-3,6-(mu-H)(2)-1,1,1-(CO)(3)-2-Ph-closo-1,2-MnCB(9)H(7)] (5b), both of which contain M'-Mn bonds. The latter reaction with M' = Pt affords [3,6-{Pt(dppe)}-3,6-(mu-H)(2)-1,1,1-(CO)(3)-2-Ph-closo-1,2-MnCB(9)H(7)] (6), which lacks a Pt-Mn connectivity. Compound 6 itself spontaneously converts to [1-Ph-2,2,2-(CO)(3)-8,8-(dppe)-hypercloso-8,2,1-PtMnCB(9)H(9)] (7b) and thence to [3,6,7-{Mn(CO)(3)}-3,7-(mu-H)(2)-1-Ph-6,6-(dppe)-closo-6,1-PtCB(8)H(6)] (8). This sequence occurs via initial insertion of the {Pt(dppe)} unit and then extrusion of {Mn(CO)(3)} and one {BH} vertex. In the presence of alcohols ROH, compound 6 is transformed to the 7-OR substituted analogues of 7b. X-ray diffraction studies were essential in elucidating the structures encountered in compounds 5-8 and hence in understanding their behavior.

  20. Dosimetric characterization of the M-15 high-dose-rate Iridium-192 brachytherapy source using the AAPM and ESTRO formalism. (United States)

    Ho Than, Minh-Tri; Munro Iii, John J; Medich, David C


    The Source Production & Equipment Co. (SPEC) model M-15 is a new Iridium-192 brachytherapy source model intended for use as a temporary high-dose-rate (HDR) brachytherapy source for the Nucletron microSelectron Classic afterloading system. The purpose of this study is to characterize this HDR source for clinical application by obtaining a complete set of Monte Carlo calculated dosimetric parameters for the M-15, as recommended by AAPM and ESTRO, for isotopes with average energies greater than 50 keV. This was accomplished by using the MCNP6 Monte Carlo code to simulate the resulting source dosimetry at various points within a pseudoinfinite water phantom. These dosimetric values next were converted into the AAPM and ESTRO dosimetry parameters and the respective statistical uncertainty in each parameter also calculated and presented. The M-15 source was modeled in an MCNP6 Monte Carlo environment using the physical source specifications provided by the manufacturer. Iridium-192 photons were uniformly generated inside the iridium core of the model M-15 with photon and secondary electron transport replicated using photoatomic cross-sectional tables supplied with MCNP6. Simulations were performed for both water and air/vacuum computer models with a total of 4 × 109 sources photon history for each simulation and the in-air photon spectrum filtered to remove low-energy photons belowδ = 10 keV. Dosimetric data, including D·(r,θ), gL(r), F(r,θ), φan(r), and φ-an, and their statistical uncertainty were calculated from the output of an MCNP model consisting of an M-15 source placed at the center of a spherical water phantom of 100 cm diameter. The air kerma strength in free space, SK, and dose rate constant, Λ, also was computed from a MCNP model with M-15 Iridium-192 source, was centered at the origin of an evacuated phantom in which a critical volume containing air at STP was added 100 cm from the source center. The reference dose rate, D·(r0,θ0) ≡ D· (1cm

  1. Geminal dianions stabilized by phosphonium substituents

    NARCIS (Netherlands)

    Harder, Sjoerd


    This review summarizes the rapid developments in the chemistry of phosphonium-stabilized group 1 and 2 methandiides, i.e. that of alkali and alkaline-earth metal bis(iminophosphorane)methandiide and bis(thiophosphorane)methandiide complexes. Apart from syntheses, structures and reactivities, also a

  2. Electronic structure of tris(2-phenylpyridine)iridium: electronically excited and ionized states (United States)

    Fine, J.; Diri, K.; Krylov, A. I.; Nemirow, C.; Lu, Z.; Wittig, C.


    A computational study of tris(2-phenylpyridine)iridium, Ir(ppy)3, is presented. The perspective is that of using organo-transition-metal complexes as phosphorescent species in light-emitting diodes (OLED's). Quantum yields approaching 100% are possible through a triplet harvesting mechanism. Complexes such as Ir(ppy)3 are amenable to exacting experimental and theoretical studies: small enough to accommodate rigor, yet large enough to support bulk phenomena in a range of host materials. The facial and meridional isomers differ by ∼220 meV, with fac-Ir(ppy)3 having the lower energy. Because fac-Ir(ppy)3 dominates in most environments, focus is on this species. Time-dependent density functional theory using long-range-corrected functionals (BNL and ωB97X) is used to calculate excited states of Ir(ppy)3 and a few low energy states of ? . The calculated T1 - S0 energy gap (2.30 eV) is in reasonable agreement with the experimental value of 2.44 eV. Only a few percent of singlet character in T1 is needed to explain so short a phosphorescence lifetime as 200 ns, because of the large ? and ? absorption cross-sections. Equilibrium geometries are calculated for S0, T1, and the lowest cation state (D0), and several ionization energies are obtained: adiabatic (5.86 eV); vertical from the S0 equilibrium geometry (5.88 eV); and vertical ionization of T1 at its equilibrium geometry (5.87 eV). These agree with a calculation by Hay (5.94 eV), and with the conservative experimental upper bound of 6.4 eV. Molecular orbitals provide qualitative explanations. A calculated UV absorption spectrum, in which transitions are vertical from the S0 equilibrium geometry, agrees with the room temperature experimental spectrum. This is consistent with Franck-Condon factors dominated by ? , as expected given the delocalized nature of the orbitals. Ir(ppy)3 vibrational frequencies were calculated and used to estimate the probability density ? for 500 K, i.e. the temperature at which the

  3. Earth Radiation Imbalance from a Constellation of 66 Iridium Satellites: Climate Science Aspects (United States)

    Wiscombe, W.; Chiu, CJ. Y.


    The "global warming hiatus" since the 1998 El Nino, highlighted by Meehl et al., and the resulting "missing energy" problem highlighted by Trenberth et al., has opened the door to a more fundamental view of climate change than mere surface air temperature. That new view is based on two variables which are strongly correlated: the rate of change of ocean heat content d(OHC)/dt; and Earth Radiation Imbalance (ERI) at the top of the atmosphere, whose guesstimated range is 0.4 to 0.9 Watts per square meters (this imbalance being mainly due to increasing CO2). The Argo float array is making better and better measurements of OHC. But existing satellite systems cannot measure ERI to even one significant digit. So, climate model predictions of ERI are used in place of real measurements of it, and the satellite data are tuned to the climate model predictions. Some oceanographers say "just depend on Argo for understanding the global warming hiatus and the missing energy", but we don't think this is a good idea because d(OHC)/dt and ERI have different time scales and are never perfectly correlated. We think the ERB community needs to step up to measuring ERI correctly, just as oceanographers have deployed Argo to measure OHC correctly. This talk will overview a proposed constellation of 66 Earth radiation budget instruments, hosted on Iridium satellites, that will actually be able to measure ERI to at least one significant digit, thus enabling a crucial test of climate models. This constellation will also be able to provide ERI at two-hourly time scales and 500-km spatial scales without extrapolations from uncalibrated narrowband geostationary instruments, using the highly successful methods of GRACE to obtain spatial resolution. This high time resolution would make ERI a synoptic variable like temperature, and allow studies of ERI's response to fast-evolving phenomena like dust storms and hurricanes and even brief excursions of Total Solar Irradiance. Time permitting, we

  4. Volcanic ash layers in blue ice fields (Beardmore Glacier Area, Antarctica): Iridium enrichments (United States)

    Koeberl, Christian


    samples, including Ir. Iridium determinations were made using INAA, with synthetical and natural (meteorite) standards. These findings are discussed.

  5. Evidence for [18-Crown-6 Na]2[S2O4] in methanol and dissociation to Na2S2O4 and 18-Crown-6 in the solid state; accounting for the scarcity of simple oxy dianion salts of alkali metal crown ethers in the solid state. (United States)

    Bruna, Pablo J; Greer, Scott; Passmore, Jack; Rautiainen, J Mikko


    [18-Crown-6 Na](2)S(2)O(4) complex was prepared in methanol solution but dissociates into 18-Crown-6 ((s)) and Na(2)S(2)O(4 (s)) on removal of the solvent. Evidence for complexation in methanol is supported by a quantitative mass analysis and the dissociation in the solid state by vibrational spectroscopy and powder X-ray diffraction. These observations are accounted for by investigating the energetics of complexation in solution and dissociation in the solid state using calculated density functional theory (DFT) gas phase binding enthalpies and free energies combined with conductor-like screening model (COSMO) solvation energies and lattice enthalpy and free energy terms derived from volume based thermodynamics (VBT). Our calculations show that complexation of alkali metal dianion salts to crown ethers are much less favorable than that of the corresponding monoanion salts in the solid state and that the formation of alkali metal crown complexes of stable simple oxy-dianion (e.g., CO(3)(2-), SO(4)(2-)) salts is unlikely. The roles of complexation with 18-Crown-6 and ion pair formation in the process of dissolution of Na(2)S(2)O(4) to methanol are discussed.

  6. 16 CFR 23.7 - Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (United States)


    ... § 23.7 Misuse of the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium,” and “osmium.” (a) It is unfair or deceptive to use the words “platinum,” “iridium,” “palladium,” “ruthenium,” “rhodium... marking or description misrepresents the product's true composition. The Platinum Group Metals (PGM)...

  7. Rhodium and iridium complexes of N-(2'-hydroxyphenyl)pyrrole-2-aldimine: Synthesis, structure, and spectral and electrochemical properties

    Indian Academy of Sciences (India)

    Semanti Basu; Indrani Pal; Ray J Butcher; Georgina Rosair; Samaresh Bhattacharya


    Reaction of N-(2'-hydroxyphenyl)pyrrole-2-aldimine (H2L) with [M(PPh3)3Cl] (M = Rh, Ir) affords complexes of type [M(PPh3)2(L)Cl]. Structures of both complexes have been determined by X-ray crystallography. In both complexes, the N-(2'-hydroxyphenyl)pyrrole-2-aldimine ligand is coordinated to the metal centre, via dissociation of the acidic protons, as a dianionic tridentate N,N,O-donor. The M(L)Cl fragment constitutes an equatorial plane with the metal at the centre and the two PPh3 ligands occupying axial positions. The complexes are diamagnetic (low-spin 6, = 0) and show intense MLCT transitions in the visible region. Cyclic voltammetry of the [M(PPh3)2(L)Cl] complexes shows reversible M(III)-M(IV) oxidation near 0.5 V vs SCE and quasi-reversible ligand-centred oxidative response near 1.0 V vs SCE.

  8. Contrasting anticancer activity of half-sandwich iridium(III) complexes bearing functionally diverse 2-phenylpyridine ligands


    Millett, Adam J.; Habtemariam, Abraha; Romero-Canelón, Isolda; Clarkson, Guy J.; Sadler, P. J.


    We report the synthesis, characterization, and antiproliferative activity of 15 iridium(III) half-sandwich complexes of the type [(η5-Cp*)Ir(2-(R′-phenyl)-R-pyridine)Cl] bearing either an electron-donating (−OH, −CH2OH, −CH3) or electron-withdrawing (−F, −CHO, −NO2) group at various positions on the 2-phenylpyridine (2-PhPy) chelating ligand giving rise to six sets of structural isomers. The X-ray crystal structures of [(η5-Cp*)Ir(2-(2′-fluorophenyl)pyridine)Cl] (1) and [(η5-Cp*)Ir(2-(4′-fluo...

  9. Iridium Cyclometalated Complexes in Host-Guest Chemistry: A Strategy for Maximizing Quantum Yield in Aqueous Media. (United States)

    Alrawashdeh, Lubna R; Cronin, Michael P; Woodward, Clifford E; Day, Anthony I; Wallace, Lynne


    The weaker emission typically seen for iridium(III) cyclometalated complexes in aqueous medium can be reversed via encapsulation in cucurbit[10]uril (Q[10]). The Q[10] cavity is shown to effectively maximize quantum yields for the complexes, compared to any other medium. This may provide significant advantages for a number of sensor applications. NMR studies show that the complexes are accommodated similarly within the host molecule, even with cationic substituents attached to the ppy ligands, indicating that the hydrophobic effect is the dominant driving force for binding. Cavity-encapsulated 1:1 host-guest species dominate the emission, but 1:2 species are also indicated, which also give some enhancement of intensity. Results demonstrate that the enhancement is due primarily to much lower rates of nonradiative decay but also suggest that the encapsulation can cause a change in character of the emitting state.

  10. New iridium complex as additive to the spiro-OMeTAD in perovskite solar cells with enhanced stability

    Directory of Open Access Journals (Sweden)

    Laura Badia


    Full Text Available A new iridium complex, IrCp*Cl(PyPyz[TFSI], has been synthesized and used as additive for the hole transporter material, spiro-OMeTAD, in perovskite solar cells. The cells prepared with this Ir additive present higher efficiency than reference cells, and similar to cells prepared with Co additive. We have determined that the presence of metal complexes as additives decreases the recombination rate, as it has been observed by impedance spectroscopy. Very interestingly, while the efficiency after 3 months decreases by 22% and 70% for reference cell and cell with Co additive, respectively, the efficiency of devices containing the Ir additive is only decreased by a 4%.

  11. Thermodestruction of complex sulfates of iridium and ruthenium in sulfate solutions at 100-180 deg C

    Energy Technology Data Exchange (ETDEWEB)

    Sinitsyn, N.M.; Godzhiev, S.E.; Blagodatin, Yu.V. (Moskovskij Inst. Tonkoj Khimicheskoj Tekhnologii (USSR))


    Thermodestruction of iridium- and ruthenium complex sulfates in sulfate solutions is studied at 100-180 deg C depending on the solution acidity, hold time, element initial chemical form in the solution, salt background. The complex ruthenium sulfates are shown to be destroyed during high-temperature solution holding with the solid phase formation, the rate of platinum metal transfer into a precipitate increasing with the temperature, hold time and pH of the source solution. Depending on the initial chemical form the thermodestruction proceeds in various ways and leads to the formation of either hydroxides or solid phase ''proper'' of the platinium metal salt. A reduced tendency to high-temperature hydrolysis of complex ruthenium sulfates at the +3 oxidation level is noted.

  12. Synthesis and photophysical properties of yellow-emitting iridium complexes. Effect of the temperature on the character of triplet emission. (United States)

    Ivanov, P; Stanimirov, S; Kaloyanova, S; Petkov, I


    The parent study includes synthesis end photophysical characterization of four new phosphorescent cyclometalated iridium (III) complexes. The cyclometaled ligands used here are 2-(4-chlorophenyl)benzo[d]thiazole, 2(4isopropylphenyl)benzo[d] thiazole, 2-(4-methoxyphenyl)benzo[d]thiazole, 4-(benzo[d]thiazol-2-yl)-N,N-dimethylaniline. The auxiliary ligand is acetylacetone (Hacac). The photometric analyses show temperature dependence on phosphorescent spectra and the nature of the emitting state of the synthesized complexes. Using fluorescent and absorption spectroscopy we suggest an explanation of the observed effect points out the transition from ligand centered (LC) to MLCT main character of the emitting state. The quantitative photometric analysis states high phosphorescent quantum yields of the complexes in solution.

  13. Structural Mimics of Phenyl Pyridine (ppy) - Substituted, Phosphorescent Cyclometalated Homo and Heteroleptic Iridium(III) Complexes for Organic Light Emitting Diodes - An Overview. (United States)

    Kajjam, Aravind Babu; Vaidyanathan, Sivakumar


    Today organic light emitting diodes are a topic of significant academic and industrial research interest. OLED technology is used in commercially available displays, and efforts have been directed to improve this technology. Design and synthesis of phosphorescent based transition metals are capable of harvesting both singlet and triplet excitons and achieve 100 % internal quantum efficiency is an active area of research. Among all the transition metals, iridium is considered a prime candidate for OLEDs due to its prominent photophysical characteristics. In the present review, we have concentrated on the Iridium based homo and heteroleptic complexes that have dissimilar substitutions on phenylpyridine ligands, different ancillary ligands and the effect of substitution on HOMO/LUMO energies and a brief discussion and correlation on the photophysical, electrochemical and device performances of the different complexes have been reviewed for organic light emitting diodes. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis of iridium and rhodium complexes with new chiral phosphine-NHC ligands based on 1,1'-binaphthyl framework and their application in asymmetric hydrogenation. (United States)

    Gu, Peng; Zhang, Jun; Xu, Qin; Shi, Min


    The first series of chiral phosphine-imidazole carbene ligands based on a 1,1'-binaphthyl framework were synthesized from (R)-2-amine-2'-(diphenylphosphino)-1,1'-binaphthyl (1) in a four-step pathway. After deprotonation of these phosphine-imidazolium salts with LiO(t)Bu, and subsequent complexation with [Ir(COD)Cl]2 and anion exchange with NaBArF, phosphine-carbene chelated iridium complexes (R)-6a and (R)-6b were obtained. Their structures have been characterized by NMR and X-ray diffraction analysis. The NHC-phosphine rhodium complex (R)-6c has been also obtained by a similar synthetic method. These iridium complexes have been applied to catalyze the asymmetric hydrogenation of alkenes to give the corresponding products in moderate to excellent conversion (up to 99%) and moderate enantioselectivities under mild conditions (up to 61% ee).

  15. A lab-on-a-molecule for anions in aqueous solution: using Kolbe electrolysis and radical methylation at iridium for sensing. (United States)

    Schmittel, Michael; Qinghai, Shu


    Iridium complex [(pq)(2)IrCl](2) (1) is established as a quantitatively operating lab-on-a-molecule in aqueous media at physiological pH. Acting as a chemodosimeter, 1 uses two channels, PL and ECL, for the detection of cyanide and acetate, with the former undergoing nucleophilic attack and the latter Kolbe electrolysis and radical-metal combination. This journal is © The Royal Society of Chemistry 2012

  16. Synthesis of Iridium(III) Carboxamides via the Bimetallic Reaction between Cp(PMe(3))IrPh(OH) and [Cp(PMe(3))Ir(Ph)NCR](+). (United States)

    Tellers, David M.; Ritter, Joachim C. M.; Bergman, Robert G.


    Reaction of Cp(PMe(3))IrPh(OH) (1) with nitriles is undetectably slow in benzene solution at room temperature. However, in the presence of Cp(PMe(3))IrPh(OTf) (2) (OTf = O(3)SCF(3)), the reaction is strongly catalyzed, leading to iridium(III) carboxamides Cp(PMe(3))IrPh[NHC(O)R] (6a-d) [R = C(6)H(4)CH(3) (6a), C(6)H(5) (6b), C(6)H(4)CF(3) (6c), CH(3) (6d)]. We propose that these transformations occur by initial displacement of the trifluoromethanesulfonate ("triflate") anion of 2 by a molecule of nitrile, leading to a nitrile-substituted iridium cation, [Cp(PMe(3))IrPh(NCR)](+) (10). Following this, the nucleophilic hydroxide group of 1 attacks the (activated) nitrile molecule bound in 10, leading (after proton transfer) to the iridium carboxamide complex. In the case of nitriles possessing hydrogens alpha to the cyano group, competitive loss of one of these protons is observed, leading to iridium C-bound cyanoenolates such as Cp(PMe(3))(Ph)Ir(CH(2)CN) (7). Protonolysis of carboxamides 6a-d with HCl yields Cp(PMe(3))IrPh(Cl) (9) and the free amides. A pronounced solvent effect is observed when the reaction between 1 and nitriles catalyzed by 2 is carried out in THF solution. The basic hydroxide ligand of 1 induces an overall dehydration/cyclization reaction of the coordinated aromatic nitrile. For example, the reaction of 1 with p-trifluorotolunitrile and a catalytic amount of 2 leads to the formation of 6c, water, [Ph(PMe(3))Ir[C(5)Me(4)CH(2)C(C(6)H(4)CF(3))N

  17. A click chemistry approach to 5,5'-disubstituted-3,3'-bisisoxazoles from dichloroglyoxime and alkynes: luminescent organometallic iridium and rhenium bisisoxazole complexes. (United States)

    van der Peet, Phillip L; Connell, Timothy U; Gunawan, Christian; White, Jonathan M; Donnelly, Paul S; Williams, Spencer J


    5,5'-Disubstituted-3,3'-bisisoxazoles are prepared in one step by the dropwise addition of aqueous potassium hydrogen carbonate to a mixture of dichloroglyoxime and terminal alkynes. The reaction exhibits a striking preference for the 5,5'-disubstituted 3,3'-bisisoxazole over the 4,5'-regioisomer. Organometallic iridium and rhenium bisisoxazole complexes are luminescent with emission wavelengths varying depending upon the identity of the 5,5'-substituent (phenyl, butyl).

  18. Highly efficient orange and red organic light-emitting diodes with iridium(III) complexes bearing benzothiazole cyclometallate ligands as emitters

    Energy Technology Data Exchange (ETDEWEB)

    Li, Ming [College of Chemistry, Sichuan University, Chengdu, 610064 (China); Wang, Qi [State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Optoelectronic Information, University of Electronic Science and Technology of China (UESTC), Chengdu, 610054 (China); Dai, Jun [College of Chemistry, Sichuan University, Chengdu, 610064 (China); Lu, Zhi-yun, E-mail: [College of Chemistry, Sichuan University, Chengdu, 610064 (China); Huang, Yan [College of Chemistry, Sichuan University, Chengdu, 610064 (China); Yu, Jun-sheng, E-mail: [State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Optoelectronic Information, University of Electronic Science and Technology of China (UESTC), Chengdu, 610054 (China); Luo, Shuai [College of Chemistry, Sichuan University, Chengdu, 610064 (China); Su, Shi-jian, E-mail: [State Key Laboratory of Luminescent Materials and Devices and Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology, Guangzhou, 510640 (China)


    Two iridium complexes bearing benzothiazole cyclometallate ligands, bis[2-(3 Prime ,5 Prime -di-tert-butylbiphenyl-4-yl)benzothiazolato-N,C{sup 2 Prime }]iridium(III) (acetylacetonate) [(tbpbt){sub 2}Ir(acac)] and bis[2-(9,9-dimethyl-9H-fluoren-2-yl)benzothiazolato-N,C{sup 2 Prime }]iridium(III) (acetylacetonate) [(fbt){sub 2}Ir(acac)], have been evaluated as orange and red electrophosphorescent materials. Both X-ray crystallographic analysis and photophysical results indicate that they possess alleviated self-quenching characteristics due to the existence of steric bulky ligands. As a result, phosphorescent organic light-emitting diodes (PhOLEDs) based on them show high performance even in heavily-doped level ({>=} 15 wt.%). The (tbpbt){sub 2}Ir(acac)-based PhOLED gives efficient orange emission with peak current efficiency of 26.9 cd/A (1280 cd/m{sup 2}) at doping ratio of 15 wt.%, while the 15 wt.% (fbt){sub 2}Ir(acac)-doped device emits efficient red light with Commission Internationale de l'Eclairage coordinates of (0.63, 0.36), and peak current and external quantum efficiency of 28.5 cd/A (1210 cd/m{sup 2}) and 15.6%, respectively. Moreover, all these heavily-doped PhOLEDs exhibit low efficiency roll-off at relatively high current density. - Highlights: Black-Right-Pointing-Pointer Two iridium complexes with bulky ligands are developed as orange/red emitter. Black-Right-Pointing-Pointer Organic light-emitting diodes using these phosphors show low efficiency roll-off. Black-Right-Pointing-Pointer High performance devices could be achieved under high doping ratio of {>=} 15 wt.%. Black-Right-Pointing-Pointer The high device efficiencies arise from the reduced self-quenching of the phosphors.

  19. Efficient H{sub 2}-producing photo-catalytic systems based on cyclo-metallated iridium- and tricarbonyl-rhenium-diimine photosensitizers and cobaloxime catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Fihri, A.; Artero, V.; Fontecave, M. [Univ Grenoble 1, Lab Chim et Biol Metaux, Grenoble (France); Fihri, A.; Artero, V.; Fontecave, M. [CNRS, UMR 5249, F-75700 Paris (France); Fihri, A.; Artero, V.; Fontecave, M. [CEA, DSV, iRTSV, F-38054 Grenoble 9 (France); Pereira, A. [CEA, DRT, Liten, DTNM, LTS, Grenoble (France)


    Quantum yield values up to 16% under visible irradiation associated with high turnover frequencies ({approx} 50 h{sup -1}) and stability (up to 273 turnovers), characterize the new photo-catalytic systems for hydrogen production, based on diimine derivatives of ruthenium, cyclo-metallated iridium or tricarbonyl-rhenium as photosensitizers and cobaloxime H{sub 2}-evolving catalytic centers, which are among the most efficient molecular systems reported so far and compete with some platinum-based systems. (authors)

  20. Ultramicroband array electrode. 1. Analysis of mercury in contaminated soils and flue gas exposed samples using a gold-plated iridium portable system by anodic stripping voltammetry. (United States)

    Xiao, Li; Dietze, William; Nyasulu, Frazier; Mibeck, Blaise A F


    The applicability of a gold-plated iridium Nano-Band array ultramicroelectrode (6 microm by 0.2 microm, 64-microm interspacing, 100 electrode bands) in the analysis of mercury using a portable system is demonstrated by anodic stripping voltammetry in real-life samples. Optimized measurement parameters, 0.1 M HCl electrolyte, plating potential of 0 mV, and staircase scan mode were identified. The dynamic linear range is 10-180 ppb at 5-s deposition time with 1.5 microC of gold plated. The experimental detection limit for Hg2+ in 0.1 M HCl was 0.5 ppb at a deposition time of 4 min and a scan rate of 10 V/s. Real-life samples, such as flue gas exposed samples from flue gas simulators could be analyzed within 5 min using the method of standard additions. We identified a field-portable extraction procedure for soil samples using 1:1 concentrated HNO3/30% H2O2 mixture, compatible with ASV and the iridium electrode. The detection limit for soils is 1 ppm. The results obtained using ASV are in good agreement with reference values using cold vapor atomic absorption for the sample matrixes studied here. To our knowledge, this is the first mercury application using a reusable iridium array ultramicroelectrode. The portable potentiostat is less than 500 g, and together with the portable digestion method, makes the Nano-Band Explorer system field applicable.

  1. (4-Chloroacetanilido-κ2N,Obis[2-(pyridin-2-ylphenyl-κ2C1,N]iridium(III

    Directory of Open Access Journals (Sweden)

    Lijun Sun


    Full Text Available In the neutral mononuclear iridium(III title compound, [Ir(C8H7ClNO(C11H8N2], the IrIII atom adopts an octahedral geometry, and is coordinated by two 2-phenylpyridyl ligands and one anionic 4-chloroacetanilide ligand. The 2-phenylpyridyl ligands are arranged in a cis-C,C′ and cis-N,N′ fashion. Each 2-phenylpyridyl ligand forms a five-membered ring with the IrIII atom. The 2-phenylpyridyl planes are perpendicular to each other [dihedral angle = 89.9 (1°]. The Ir—C and Ir—N bond lengths are comparable to those reported for related iridium(III 2-phenylpyridyl complexes. The remaining two coordination sites are occupied by the amidate N and O atoms, which form a four-membered ring with the iridium atom (Ir—N—C—O. The amidate plane is nearly perpendicular to both 2-phenylpyridyl ligands [dihedral angles = 87.8 (2 and 88.3 (2°].

  2. A cyclometalated iridium(III) complex with enhanced phosphorescence emission in the solid state (EPESS): synthesis, characterization and its application in bioimaging. (United States)

    Wu, Huazhou; Yang, Tianshe; Zhao, Qiang; Zhou, Jing; Li, Chunyan; Li, Fuyou


    Iridium(III) complexes with intense phosphorescence in solution have been widely applied in organic light-emitting diodes, chemosensors and bioimaging. However, little attention has been paid to iridium(III) complexes showing weak phosphorescence in solution and enhanced phosphorescence emission in the solid state (EPESS). In the present study, two β-diketonate ligands with different degrees of conjugation, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HL1) and 1-phenyl-3-methyl-4-phenylacetyl-5-pyrazolone (HL2), have been synthesized to be used as ancillary ligands for two iridium(III) complexes, Ir(ppy)(2)(L1) and Ir(ppy)(2)(L2) (Hppy = 2-phenylpyridine). The two complexes have been characterized by single-crystal X-ray crystallography, (1)H NMR and elemental analysis. Interestingly, Ir(ppy)(2)(L1) is EPESS-active whereas Ir(ppy)(2)(L2) exhibits moderately intense emission both in solution and as a neat film, indicating that the degree of conjugation of the β-diketone ligands determines the EPESS-activity. The single-crystal X-ray analysis has indicated that there are π-π interactions between the adjacent ppy ligands in Ir(ppy)(2)(L1) but not in Ir(ppy)(2)(L2). Finally, EPESS-active Ir(ppy)(2)(L1) has been successfully embedded in polymer nanoparticles and used as a luminescent label in bioimaging.

  3. Local Delivery of C-myc Antisense Oligodeoxynucleotide by Gelatin Coated Platinium-Iridium Stent to Prevent Restenosis in a Normal Rabbit Carotid Artery

    Institute of Scientific and Technical Information of China (English)

    Zhang Xinxia; Wei Wenbin; Duan Wen; Xu Xiangguang; Hu Xuesong


    Objectives To investigate the feasibility and effect of local deliveryof c-myc antisense oligodeoxynucleotide (ASODN) by gelatin coated Platinium-Iridium stent to prevent restenosis in a normal rabbit carotid artery. Methods Gelatin coated Platinium-Iridium stent were implanted in the right carotid arteries of 32 rabbits under vision. Animals were randomized to the control group and the treated group receiving c-myc ASODN (n=16 respectively).7,14,30,90 days following the stenting procedure,morphometry for caculation of neointimal area and mean neointimal thickness were performed.The expression of c-myc protein was detected by immunohistochemical methods. Results 32 stents were successfully implanted into the right carotid arteries in 32 animals. Morphometric analysis showed that neointimal area and mean neointimal thickness siginificantly increased continuously up to 12 weeks after stent implantation,and at each time point ,neointimal area and mean neointimal thickness were siginificantly smaller in the treated group than control group. (P<0.001 ,respectively).c-myc protein expression was weak positive or negative in treated group and positive in control group. Conclusions Gelatin coated Platinium-Iridium stent mediated local delivery of c-myc ASODN is feasibility , and it can inhibit neointimal hyperplasia to prevent restenosis in a normal rabbit carotid artery.

  4. A magnetism-based approach to examining spin-orbit coupling effects in solid systems of isolated iridium octahedra (United States)

    Phelan, Brendan F.

    This thesis explores the relative strengths of Spin-Orbit Coupling (SOC) in several perovskite-like systems that feature uninterrupted arrays of isolated IrO6 octahedra. Iridate compounds are particularly interesting to the community due to their relevance to emergent material properties such as insulating antiferromagnets, superconductors, and topological insulators. Recently literature has pointed to a complex interaction between SOC and crystal field splitting (CFS) in d5 metals. I utilize a straightforward, magnetic approach to determine the relative strengths of SOC vs CFS by chemically modifying structure and oxidation state. This contrasts with other work where advanced spectroscopic measurements are utilized to probe energy levels within a single compound. The focus of this study lies in two main methodologies: 1) Tracking the evolution of the Ir magnetic moment on progressing from 5 d5 Ir4+ to 5d 4 Ir5+ oxidation states that are clearly best described by a transition from a J=1/2 to a J=0 Ir magnetic state. In these cases, the evolution of the magnetic susceptibility shows the dominance of spin-orbit coupling in determining the magnetic properties of a material with highly isolated IrO6 octahedra. 2) Distorting J=0 Ir5+ systems where there is no emergence of an enhanced magnetic moment in the series on increasing the structural distortions, as would have been the case for significant crystal field splitting that reinforces the notion that spin-orbit coupling is the dominant force in determining the magnetism of iridium-oxygen octahedra in perovskite-like structures. The organization of this thesis is as follows: Chapter 1 presents a brief introduction to solid-state chemistry, iridates, and magnetism. Chapter 2 is an overview of experimental methodology and instrumentation. Chapter 3, presents a study of tuning the oxidation state of a new structure type: SrxLa11-xIr4O24. Chapter 4 presents a structural tuning of the Ir5+ system: Ba 2-xSrxYIrO6. Finally

  5. Metal-ligand cooperation in catalytic intramolecular hydroamination: a computational study of iridium-pyrazolato cooperative activation of aminoalkenes. (United States)

    Tobisch, Sven


    The present study comprehensively explores diverse mechanistic pathways for intramolecular hydroamination of prototype 2,2-dimethyl-4-penten-1-amine by Cp*Ir chloropyrazole (1; Cp*=pentamethylcyclopentadienyl) in the presence of KOtBu base with the aid of density functional theory (DFT) calculations. The most accessible mechanistic pathway for catalytic turnover commences from Cp*Ir pyrazolato (Pz) substrate adduct 2⋅S, representing the catalytically competent compound and proceeds via initial electrophilic activation of the olefin C=C bond by the metal centre. It entails 1) facile and reversible anti nucleophilic amine attack on the iridium-olefin linkage; 2) Ir-C bond protonolysis via stepwise transfer of the ammonium N-H proton at the zwitterionic [Cp*IrPz-alkyl] intermediate onto the metal that is linked to turnover-limiting, reductive, cycloamine elimination commencing from a high-energy, metastable [Cp*IrPz-hydrido-alkyl] species; and 3) subsequent facile cycloamine liberation to regenerate the active catalyst species. The amine-iridium bound 2 a⋅S likely corresponds to the catalyst resting state and the catalytic reaction is expected to proceed with a significant primary kinetic isotope. This study unveils the vital role of a supportive hydrogen-bonded network involving suitably aligned β-basic pyrazolato and cycloamido moieties together with an external amine molecule in facilitating metal protonation and reductive elimination. Cooperative hydrogen bonding thus appears pivotal for effective catalysis. The mechanistic scenario is consonant with catalyst performance data and furthermore accounts for the variation in performance for [Cp*IrPz] compounds featuring a β- or γ-basic pyrazolato unit. As far as the route that involves amine N-H bond activation is concerned, a thus far undocumented pathway for concerted amidoalkene → cycloamine conversion through olefin protonation by the pyrazole N-H concurrent with N-C ring closure is disclosed as a

  6. Diamonds from the iridium-rich K-T boundary layer at Arroyo el Mimbral, Tamaulipas, Mexico (United States)

    Hough, R. M.; Gilmour, I.; Pillinger, C. T.; Langenhorst, F.; Montanari, A.


    Diamonds, up to 30 μm in size, were found in the iridium-rich layer from the K-T boundary site at Arroyo El Mimbral and the spherule bed from Arroyo El Peñon, northeastern Mexico. Stepped heating experiments indicate two or more isotopically distinct diamond components with carbon isotopic compositions characteristic of a mixture of carbon sources. The diamonds' crystal form is cubic—not the hexagonal polymorph of diamond, lonsdaleite, which has been used previously to infer formation due to shock transformation of graphite. The size, crystallography, and mineralogic associations of K-T diamonds are similar to those of impact-produced diamonds from the Ries crater in Germany where both shock transformation of graphite and a mode of formation by condensation from a vapor plume have been inferred. The discovery of impact-produced diamonds in association with high Ir contents for these sediments supports their impact origin, K-T age, and the inference that their source was from the buried impact crater of Chicxulub on the Yucatan peninsula, Mexico.

  7. Theoretical studies on the regioselectivity of iridium-catalyzed 1,3-dipolar azide-alkyne cycloaddition reactions. (United States)

    Luo, Qiong; Jia, Guochen; Sun, Jianwei; Lin, Zhenyang


    Iridium-catalyzed cycloaddition of thioalkynes and bromoalkynes with azides have been investigated with the aid of density functional theory (DFT) calculations at the M06 level of theory. Our investigation focused on the different regioselectivity observed for the reactions of the two classes of alkynes. The DFT results have shown that the mechanisms of cycloaddition reactions using thioalkynes and bromoalkynes as substrates are similar yet different. The reactions of thioalkynes occur via a metallabicyclic Ir-carbene intermediate formed through alkyne-azide oxidative coupling via attack of the azide terminal nitrogen toward the β alkyne carbon, whose carbene ligand is stabilized by an alkylthio/arylthio substituent. Reductive elimination from the intermediate leads to the formation of the experimentally observed 5-sulfenyltriazole. In the reactions of bromoalkynes RC≡CBr, the reaction mechanism involves the initial formation of a six-membered-ring metallacycle intermediate in the oxidative coupling step. The six-membered-ring intermediate then undergoes isomerization via migrating the terminal azide nitrogen from the β carbon to the α carbon to form a much less stable metallabicyclic Ir-carbene species from which reductive elimination gives 4-bromotriazole.

  8. Kinetics and Mechanism of Iridium(Ⅲ)-Catalyzed Oxidation of Ethanol Amine by Cerium(Ⅳ) in Sulfuric Acid Media

    Institute of Scientific and Technical Information of China (English)

    ZHAI Yong-qing; LIU Hong-mei; YANG Lin; YANG Guo-zhong; SONG Wen-yu; LIU Yu-kai


    In this study, the kinetics and mechanism of the iridium(Ⅲ)-catalyzed oxidation of ethanol amine(EAN) by cerium(Ⅳ) in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298-313 K. It was found that the reaction is of first order with respect to Ce(Ⅳ) and Ir(Ⅲ), and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order([EAN](》)[Ce(Ⅳ)]) rate constant kobs decreases with the increase of [H+] and [HSO-4]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of kobs on the concentration of hydrogen sulfate, Ce(SO4)2 was found to be the kinetically active species. The rate constants of the rate-determining step together with the activation parameters were evaluated.

  9. Development of biosensor for phenolic compounds containing PPO in β-cyclodextrin modified support and iridium nanoparticles. (United States)

    da Silva, Cristiano P; Franzoi, Ana C; Fernandes, Suellen C; Dupont, Jairton; Vieira, Iolanda C


    A biosensor based on the iridium nanoparticles dispersed in ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (Ir-BMI·PF6) and a celery (Apium graveolens) extract as a source of polyphenol oxidase (PPO) was constructed. A modified support based on β-cyclodextrin (β-CDEP) was used for enzyme immobilization. The behavior of phenolic compounds was investigated by square-wave voltammetry and rutin was selected by presenting the greatest signal. The best performance was obtained with a composition of 70:10:10:10% (w/w/w/w) of the graphite powder:β-CDEP:Nujol:Ir-BMI·PF6 composition, a PPO concentration of 500unitsmL(-1), in 0.1M phosphate buffer solution (pH 6.0) with frequency, pulse amplitude and scan increment at 100Hz, 60mV, and 3.0mV, respectively. Under optimized conditions, the cathodic currents increased linearly for the rutin concentration range of 1.3×10(-7)-2.0×10(-6)M with a detection limit of 7.9×10(-8)M. This sensor demonstrated acceptable repeatability and reproducibility and the results for the rutin recovery ranged from 92.8 to 103.4%. A relative error of 0.7% was obtained in the rutin determination in simulated samples.

  10. A study of the electrochemical behavior in tungsten and caustic solutions and platinum/iridium in chloride solutions, informal report

    Energy Technology Data Exchange (ETDEWEB)

    Vitus, C.M.; Isaacs, H.S. [Brookhaven National Lab., Upton, NY (United States); Schroeder, V. [Univ. of California, Berkeley, CA (United States). College of Engineering


    Platinum/iridium and tungsten wires were electronically etched in chloride and caustic solution, respectively, to produce tips with high aspect ratio. A direct relationship between the meniscus and the aspect ratio of etched tips was established. Scanning electron micrographs indicated that higher aspect ratios were obtained by changing the geometry of the meniscus during the etch either by an increase in the applied a.c. voltage or with the addition of a nonpolar layer above the electrolytic solution during the etching process. Above the breakdown voltage, two possible mechanisms appeared to control the etching process by expediting chemical dissolution: cavitation and sparking. Cavitation caused erosion due to the force of evolved gases against the electrode and sparking attacked the surface by vaporizing the metal. Sparking commenced on both wires near 24V. This voltage corresponded to a minimum in the plot of total etch time versus voltage. From light emission studies, sparking on Pt/Ir was associated with the ionization of Pt, Ir, Ca, and Cl. A compositional analysis of insoluble black particles produced during a.c. and d.c. etching of Pt/Ir revealed Pt and Ir as the major constituents of the product. The sparking process was shown to have a potential use in micromachining.

  11. Effects of Molecular Oxygen, Solvent, and Light on Iridium-Photoredox/Nickel Dual-Catalyzed Cross-Coupling Reactions. (United States)

    Oderinde, Martins S; Varela-Alvarez, Adrian; Aquila, Brian; Robbins, Daniel W; Johannes, Jeffrey W


    In order to achieve reproducibility during iridium-photoredox and nickel dual-catalyzed sp(3)-sp(2) carbon-carbon bond-forming reactions, we investigated the role that molecular oxygen (O2), solvent and light-source (CF lamp or blue LED) play in a variety of Ir-photoredox mediated transformations. The presence of O2 was discovered to be important for catalyst activation when air-stable Ni(II) precatalysts were used in DMF under CF lamp irradiation; however, O2 was not required for catalysis when conducted with Ni(COD)2 in the same reaction system. O2 is believed to promote rapid reduction of the Ni(II) precatalyst by Ir(II) to Ni(0). In addition to O2, the effects that solvent and light-source have on the dual-catalyzed decarboxylative cross-coupling reactions will be discussed. These findings have enabled us to develop a more robust dual-catalyzed decarboxylative cross-coupling protocol.

  12. Iridium-Catalyzed Asymmetric Hydrogenation of Olefins with Chiral N,P and C,N Ligands (United States)

    Woodmansee, David H.; Pfaltz, Andreas

    Asymmetric hydrogenation is one of the most important catalytic methods for the preparation of optically active compounds. For a long time, chiral rhodium- and ruthenium-diphosphine complexes were the catalysts of choice in this field. However, their application range in the asymmetric hydrogenation of olefins is limited to substrates bearing a coordinating group adjacent to the C=C bond. These limitations were surmounted with the advent of iridium complexes with chiral N,P-ligands. For a wide range of unfunctionalized olefins, excellent enantioselectivities can now be achieved with low catalyst loadings. Moreover, these catalysts also allow highly enantioselective hydrogenation of various functionalized olefins, heterocycles such as furans or indoles, and imines. Research in this field is productive with new catalysts giving high enantioselectivities for difficult substrates appearing at an ever more frequent rate. These methods greatly expand the repertoire of reactions available to synthetic chemists for the preparation of optically active compounds in a reliable and an atom-economical fashion.

  13. Homogeneous water oxidation by half-sandwich iridium(III)NHC complexes with pendant hydroxy and amino groups. (United States)

    Mahanti, Bani; González Miera, Greco; Martínez-Castro, Elisa; Bedin, Michele; Martín-Matute, Belén; Ott, Sascha; Thapper, Anders


    Herein we report three Ir(III)Cp* complexes with hydroxy- (1, 2) or amino- (3) functionalized N-heterocyclic carbene (NHC) ligands as catalysts for efficient water oxidation induced by addition of ceric ammonium nitrate (CAN). The pendant hydroxy- or amino- groups are very important for activity and the complexes with heteroatom-functionalized NHC ligands show up to 15 times higher rate of oxygen evolution in CAN-induced water oxidation compared to a reference Ir(III)Cp* complex without heteroatom functionalization (4). The presence of molecular high-valent Ir intermediates that are presumably involved in the rate-determining step for water oxidation is established by UV-vis spectroscopic and ESI mass spectrometric analyses during turnover conditions. The hydroxy-groups on the NHC ligands, as well as chloride ligands on the iridium center are proposed to structurally stabilize the high-valent species, and thereby improve the catalytic activity. The Ir(III) complex 1 with a hydroxy-functionalized NHC shows the highest catalytic activity with a TON of 2500 obtained in 3 h and with >90% yield relative to the amount of used oxidant. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Iridium oxide pH sensor for biomedical applications. Case urea-urease in real urine samples. (United States)

    Prats-Alfonso, Elisabet; Abad, Llibertat; Casañ-Pastor, Nieves; Gonzalo-Ruiz, Javier; Baldrich, Eva


    This work demonstrates the implementation of iridium oxide films (IROF) grown on silicon-based thin-film platinum microelectrodes, their utilization as a pH sensor, and their successful formatting into a urea pH sensor. In this context, Pt electrodes were fabricated on Silicon by using standard photolithography and lift-off procedures and IROF thin films were growth by a dynamic oxidation electrodeposition method (AEIROF). The AEIROF pH sensor reported showed a super-Nerstian (72.9±0.9mV/pH) response between pH 3 and 11, with residual standard deviation of both repeatability and reproducibility below 5%, and resolution of 0.03 pH units. For their application as urea pH sensors, AEIROF electrodes were reversibly modified with urease-coated magnetic microparticles (MP) using a magnet. The urea pH sensor provided fast detection of urea between 78μM and 20mM in saline solution, in sample volumes of just 50μL. The applicability to urea determination in real urine samples is discussed.

  15. Ultrathin Vein-Like Iridium-Tin Nanowires with Abundant Oxidized Tin as High-Performance Ethanol Oxidation Electrocatalysts. (United States)

    Zhu, Meiwu; Shao, Qi; Pi, Yecan; Guo, Jun; Huang, Bin; Qian, Yong; Huang, Xiaoqing


    Iridium (Ir) holds great promise for ethanol oxidation reaction (EOR), while its practical applications suffer from the limited shape-controlled synthesis due to its low-energy barrier for nucleation. To overcome this limitation, the preparation of a new class of ultrathin vein-like Ir-tin nanowires (IrSn NWs) with abundant oxidized Sn is reported. By tuning the ratio of Ir to Sn, the optimized Ir67 Sn33 /C exhibits the highest mass density of 95.6 mA mg(-1) Ir for EOR at low potential (0.04 V), which is 4.1-fold and 20-fold higher than that of Ir/C and the commercial Pt/C, respectively. It also exhibits the smallest Tafel slope of 153 mV dec(-1) and superior stability after 2 h chronoamperometric measurement. Electrochemical measurements and X-ray photoelectron spectra results confirm that the abundant oxidized Sn promotes a complete oxidization of ethanol into CO2 at low potential. This work highlights the importance of non-noble metal on enhancing the EOR performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. T1-relaxation of 129Xe on metal single crystal surfaces—multilayer experiments on iridium and monolayer considerations (United States)

    Stahl, Dirk; Mannstadt, Wolfgang; Gerhard, Peter; Koch, Matthias; Jänsch, Heinz J.


    The surface of a typical laboratory single crystal has about 10 15 surface atoms or adsorption sites, respectively, and is thus far out of reach for conventional NMR experiments using thermal polarization. It should however be in reach for NMR of adsorbed laser polarized (hyperpolarized) 129Xe, which is produced by spin transfer from optically pumped rubidium. With multilayer experiments of xenon adsorbed on an iridium surface we do not only demonstrate that monolayer sensitivity has been obtained, we also show that such surface experiments can be performed under ultra high vacuum conditions with the crystal being mounted in a typical surface analysis chamber on a manipulator with far-reaching sample heating and cooling abilities. With only four spectra summed up we present an NMR signal from at most 4×10 14 atoms of 129Xe, four layers of naturally abundant xenon, respectively. The fact that no monolayer signal has been measured so far is explained by a fast Korringa relaxation due to the Fermi contact interaction of the 129Xe nuclei with the electrons of the metal substrate. T1-relaxation times in the order of several ms have been calculated using all electron density functional theory for several metal substrates.

  17. Red phosphorescent organic light-emitting diodes (PhOLEDs) based on a heteroleptic cyclometalated Iridium (III) complex

    Energy Technology Data Exchange (ETDEWEB)

    Lepeltier, Marc [Institut Lavoisier de Versailles, UMR 8180 CNRS, Université de Versailles Saint-Quentin en Yvelines, 45 avenue des Etats-Unis, 78035 Versailles Cedex (France); Dumur, Frédéric, E-mail: [Aix-Marseille Université, CNRS, ICR, UMR 7273, F-13397 Marseille (France); Wantz, Guillaume, E-mail: [University of Bordeaux, IMS, UMR 5218, F-33400 Talence (France); CNRS, IMS, UMR 5218, F-33400 Talence (France); Vila, Neus; Mbomekallé, Israel [Institut Lavoisier de Versailles, UMR 8180 CNRS, Université de Versailles Saint-Quentin en Yvelines, 45 avenue des Etats-Unis, 78035 Versailles Cedex (France); Bertin, Denis; Gigmes, Didier [Aix-Marseille Université, CNRS, ICR, UMR 7273, F-13397 Marseille (France); Mayer, Cédric R., E-mail: [Laboratoire d’Ingénierie des Systèmes de Versailles LISV – EA 4048, Université de Versailles Saint Quentin en Yvelines, 10/12 avenue de l’Europe, 78140 Vélizy (France)


    Highly efficient red-emitting Phosphorescent Organic Light-Emitting Diodes (PhOLEDs) based on a neutral vacuum-sublimatable heteroleptic iridium (III) complex have been designed and studied. Heteroleptic complex Ir(piq){sub 2}(acac) was prepared in one step with acetylacetone (acac) as the ancillary ligand. Electronic and spectroscopic properties of Ir(piq){sub 2}(acac) were investigated by UV–visible absorption, fluorescence spectroscopy and cyclic voltammetry. Electrophosphorescent devices comprising Ir(piq){sub 2}(acac) as dopant of TCTA exhibited outstanding electroluminescence performance with a current efficiency of 10.0 cd A{sup −1}, a maximum power efficiency of 7.2 lm W{sup −1} and a maximal brightness of 3540 cd m{sup −2} was reached at 8.0 V. CIE coordinates close to the standard red of the national television system committee were obtained (0.67, 0.33). -- Highlights: • A saturated red OLED has been prepared. • High power efficiency and brightness were obtained. • Thickness of the device was determined as a parameter determining the overall performance. • CIE coordinates close to the standard red of the national television system committee were obtained.

  18. Crystal structures of fac-trichloridotris(trimethylphosphane-κPrhodium(III monohydrate and fac-trichloridotris(trimethylphosphane-κPrhodium(III methanol hemisolvate: rhodium structures that are isotypic with their iridium analogs

    Directory of Open Access Journals (Sweden)

    Joseph S. Merola


    Full Text Available The crystal structures of two solvates of fac-trichloridotris(trimethylphosphane-κPrhodium(III are reported, i.e. one with water in the crystal lattice, fac-[RhCl3(Me3P3]·H2O, and one with methanol in the crystal lattice, fac-[RhCl3(Me3P3]·0.5CH3OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al. (2013. Polyhedron, 54, 67–73]. Comparison is made between the rhodium and iridium compounds, highlighting their isostructural relationships.

  19. Highly potent extranuclear-targeted luminescent iridium(iii) antitumor agents containing benzimidazole-based ligands with a handle for functionalization. (United States)

    Yellol, Jyoti; Pérez, Sergio A; Yellol, Gorakh; Zajac, Juraj; Donaire, Antonio; Vigueras, Gloria; Novohradsky, Vojtech; Janiak, Christoph; Brabec, Viktor; Ruiz, José


    A series of 6 substitutionally inert and luminescent iridium(iii) antitumor agents of the type [Ir(C(∧)N)2(N(∧)N)][PF6] containing a benzimidazole N(∧)N ligand with an ester group as a handle for further functionalization has been prepared. They exhibit IC50 values in the high nanomolar range in some ovarian and breast cancer cell lines (approximately 100× more cytotoxic than cisplatin (CDDP) in MDA-MB-231) and are located in the actin cortex predominantly as shown by confocal luminescence microscopy. This discovery could open the door to a new large family of drug bioconjugates with diverse and simultaneous functions.

  20. Iridium-catalyzed ortho-selective C-H silylation of aromatic compounds directed toward the synthesis of π-conjugated molecules with Lewis acid-base interaction. (United States)

    Wakaki, Takayuki; Kanai, Motomu; Kuninobu, Yoichiro


    We successfully developed an iridium-catalyzed ortho-selective C-H silylation of aromatic compounds. The reaction exhibited a wide substrate scope, and a variety of π-conjugated molecules were synthesized in good to excellent yields, even in gram scale. Several silyl groups could also be introduced into the products. The experimental results indicated that the regioselectivity could be controlled by a Lewis acid-base interaction between the Lewis acidic silicon atoms of fluorinated hydrosilanes and the Lewis basic nitrogen atoms of aromatic compounds.

  1. Mechanism of dicarbonyl(2,4-pentanedionato)iridium(I) decomposition on iron surface and in gas phase: Complex experimental and theoretical study (United States)

    Kovaleva, Evgenia A.; Kuzubov, Alexander A.; Vikulova, Evgeniia S.; Basova, Tamara V.; Morozova, Natalya B.


    The mechanism of thermal destruction of Ir(acac)(CO)2 as one of the most important MOCVD precursors for Ir coatings deposition was proposed on the footing of the in situ mass spectrometry analysis and quantum chemical modeling. Calculated structural parameters and vibrational spectra of Ir(acac)(CO)2 molecule were found to be in a fairly good agreement with the experimental data. Ir(acac)(CO)2 was found to unlikely decompose in the gaseous phase while its adsorption onto the iron surface leads to major structural distortions easing the bond cleavage, molecule decomposition with subsequent formation of iridium films.

  2. Novel iridium(III) complexes based on 2-(2,2’-bithien-5-yl)-quinoline. Synthesis, photophysical, photochemical and DFT studies

    Energy Technology Data Exchange (ETDEWEB)

    Szafraniec-Gorol, Grażyna, E-mail: [Institute of Chemistry, Faculty of Mathematics, Physics and Chemistry, University of Silesia, Szkolna 9, 40-007 Katowice (Poland); Słodek, Aneta; Filapek, Michał [Institute of Chemistry, Faculty of Mathematics, Physics and Chemistry, University of Silesia, Szkolna 9, 40-007 Katowice (Poland); Boharewicz, Bartosz; Iwan, Agnieszka [Electrotechnical Institute, Division of Electrotechnology and Materials Science, M. Sklodowskiej-Curie 55/61, 50-369 Wroclaw (Poland); Jaworska, Maria; Żur, Lidia; Sołtys, Marta; Pisarska, Joanna; Grudzka-Flak, Iwona [Institute of Chemistry, Faculty of Mathematics, Physics and Chemistry, University of Silesia, Szkolna 9, 40-007 Katowice (Poland); Czajkowska, Sylwia [Centre of Polymer and Carbon Materials, Polish Academy of Sciences, M. Curie-Sklodowskiej 34, 41-819 Zabrze (Poland); Sojka, Maciej; Danikiewicz, Witold [Institute of Organic Chemistry, Polish Academy of Science, Kasprzaka 44/52, 01-224 Warsaw (Poland); Krompiec, Stanisław [Institute of Chemistry, Faculty of Mathematics, Physics and Chemistry, University of Silesia, Szkolna 9, 40-007 Katowice (Poland)


    Four novel cyclometalated iridium(III) complexes: [Ir(q-bt-Ph){sub 2}(phen)]PF{sub 6}, [Ir(q-bt-Ph){sub 2}(acac)], [Ir(q-bt-Me){sub 2}(bpy)]PF{sub 6} and [Ir(q-bt-Me){sub 2}(acac)] (where q-bt-Ph, q-bt-Me correspond to 2-(2,2’-bithien-5-yl)-4-phenylquinoline and 2-(2,2’-bithien-5-yl)-4-methylquinoline), are reported. The complexes were characterized by NMR, FTIR and HRMS. The optical, electrochemical properties and thermal stability of novel iridium(III) complexes were thoroughly investigated. The complexes emit a light in the narrow range of 693–707 nm. The optical study showed that replacement of fragment in the main quinoline ligand did not affect wavelength of the emitted light. On the other hand, the modification of the ancillary ligand and substituent in the quinoline ring caused the increase of the photoluminescence quantum yields. Electrochemical experiments demonstrate that the oxidation process for complexes [Ir(q-bt-Ph){sub 2}(phen)]PF{sub 6} and [Ir(q-bt-Ph){sub 2}(acac)] was reversible (or quasi-reversible) and well detectable whereas for complexes with quinoline substituted by methyl group was irreversible, even at low temperature (−70 °C). The electrochemical and photophysical studies have been well confirmed by density functional theory (DFT) calculations. In addition, bulk heterojunction polymer solar cells based on complexes [Ir(q-bt-Ph){sub 2}(phen)]PF{sub 6} and [Ir(q-bt-Ph){sub 2}(acac)] were fabricated. Only the solar cell incorporating [Ir(q-bt-Ph){sub 2}(acac)] exhibited a photovoltaic effect. The architecture of the cell was ITO/PEDOT:PSS/P3HT:PCBM:[Ir(q-bt-Ph){sub 2}(acac)]/Al. A power conversion efficiency of 0.25% was measured under 1 sun illumination using an AM 1.5G filter to simulate the solar spectrum. - Graphical abstract: Display Omitted - Highlights: • Iridium(III) complexes bearing 2-bithienylquinolines as main ligands were examined. • Optical and electrochemical measurements were compared with DFT calculations.

  3. The discovery of half-sandwich iridium complexes containing lidocaine and (pyren-1-yl)ethynyl derivatives of phenylcyanamide ligands for photodynamic therapy. (United States)

    Tabrizi, Leila


    The successful design, synthesis, characterization, photophysical properties and anticancer mechanistic studies of a series of half-sandwich cyclopentadienyl iridium(iii) complexes of the type [Cp*Ir(III)(LC)(L1)](PF6), 1, and [Cp*Ir(III)(LC)(L2)](PF6), 2, in which Cp* = pentamethylcyclopentadienyl, L1 = 4-(pyren-10-yl)ethynyl-phenylcyanamide, L2 = 4'-(pyren-10-yl)ethynyl-4-cyanamidobiphenyl, and LC = lidocaine, are reported for their application as photodynamic therapy (PDT) agents. The DNA binding, DNA photocleavage, cellular uptake, and apoptosis of the complexes have also been studied.

  4. A configurational switch based on iridium-catalyzed allylic cyclization: application in asymmetric total syntheses of prosopis, dendrobate, and spruce alkaloids. (United States)

    Gnamm, Christian; Brödner, Kerstin; Krauter, Caroline M; Helmchen, Günter


    A method for the stereoselective synthesis of 2,6-disubstituted piperidines has been developed that is based on the use of an intramolecular iridium-catalyzed allylic substitution as a configurational switch. The procedure allows the preparation of 2-vinylpiperidines with enantiomeric excesses (ee) of greater than 99%. As applications, total syntheses of piperidine alkaloids have been elaborated, most often by using Ru-catalyzed cross-metatheses as a key step for introduction of a side chain. Asymmetric total syntheses of the prosopis alkaloids (+)-prosopinine, (+)-prosophylline, (+)-prosopine, and of the dendrobate alkaloid (+)-241D and its C6 epimer are described.

  5. Basic ancillary ligands promote O-O bond formation in iridium-catalyzed water oxidation: a DFT study. (United States)

    Vilella, Laia; Vidossich, Pietro; Balcells, David; Lledós, Agustí


    The cationic iridium complex [Ir(OH(2))(2)(phpy)(2)](+) (phpy = o-phenylpyridine) is among the most efficient mononuclear catalysts for water oxidation. The postulated active species is the oxo complex [Ir(O)(X)(phpy)(2)](n), with X = OH(2) (n = +1), OH(-) (n = 0) or O(2-) (n = -1), depending on the pH. The reactivity of these species has been studied computationally at the DFT(B3LYP) level. The three [Ir(O)(X)(phpy)(2)](n) complexes have an electrophilic Ir(v)-oxo moiety, which yields an O-O bond by undergoing a nucleophilic attack of water in the critical step of the mechanism. In this step, water transfers one proton to either the Ir(V)-oxo moiety or the ancillary X ligand. Five different reaction pathways associated with this acid/base mechanism have been characterized. The calculations show that the proton is preferably accepted by the X ligand, which plays a key role in the reaction. The higher the basicity of X, the lower the energy barrier associated with O-O bond formation. The anionic species, [Ir(O)(2)(phpy)(2)](-), which has the less electrophilic Ir(V)-oxo moiety but the most basic X ligand, promotes O-O bond formation through the lowest energy barrier, 14.5 kcal mol(-1). The other two active species, [Ir(O)(OH)(phpy)(2)] and [Ir(O)(OH(2))(phpy)(2)](+), which have more electrophilic Ir(V)-oxo moieties but less basic X ligands, involve higher energy barriers, 20.2 kcal mol(-1) and 25.9 kcal mol(-1), respectively. These results are in good agreement with experiments showing important pH effects in similar catalytic systems. The theoretical insight given by the present study can be useful in the design of more efficient water oxidation catalysts. The catalytic activity may increase by using ligand scaffolds bearing internal bases.

  6. Effect of thermal treatment on the characteristics of iridium Schottky barrier diodes on n-Ge (1 0 0)

    Energy Technology Data Exchange (ETDEWEB)

    Chawanda, A., E-mail: [Department of Physics, University of Pretoria, 0002 (South Africa); Department of Physics, Midlands State University, Bag 9055, Gweru (Zimbabwe); Coelho, S.M.M.; Auret, F.D.; Mtangi, W. [Department of Physics, University of Pretoria, 0002 (South Africa); Nyamhere, C. [Department of Physics, Nelson Mandela Metropolitan University, Box 77000, Port Elizabeth 6031 (South Africa); Nel, J.M.; Diale, M. [Department of Physics, University of Pretoria, 0002 (South Africa)


    Highlights: Black-Right-Pointing-Pointer Ir/n-Ge (1 0 0) Schottky diodes were characterized using I-V, C-V and SEM techniques under various annealing conditions. Black-Right-Pointing-Pointer The variation of the electrical and structural properties can be due to effects phase transformation during annealing. Black-Right-Pointing-Pointer Thermal stability of these diodes is maintained up to 500 Degree-Sign C anneal. Black-Right-Pointing-Pointer SEM results depicts that the onset temperature for agglomeration in 20 nm Ir/n-Ge (1 0 0) system occurs between 600 and 700 Degree-Sign C. - Abstract: Iridium (Ir) Schottky barrier diodes were deposited on bulk grown (1 0 0) Sb-doped n-type germanium by using the electron beam deposition system. Electrical characterization of these contacts using current-voltage (I-V) and capacitance-voltage (C-V) measurements was performed under various annealing conditions. The variation of the electrical properties of these Schottky diodes can be attributed to combined effects of interfacial reaction and phase transformation during the annealing process. Thermal stability of the Ir/n-Ge (1 0 0) was observed up to annealing temperature of 500 Degree-Sign C. Furthermore, structural characterization of these samples was performed by using a scanning electron microscopy (SEM) at different annealing temperatures. Results have also revealed that the onset temperature for agglomeration in a 20 nm Ir/n-Ge (1 0 0) system occurs between 600 and 700 Degree-Sign C.

  7. Rhodium, iridium and nickel complexes with a 1,3,5-triphenylbenzene tris-MIC ligand. Study of the electronic properties and catalytic activities

    Directory of Open Access Journals (Sweden)

    Carmen Mejuto


    Full Text Available The coordination versatility of a 1,3,5-triphenylbenzene-tris-mesoionic carbene ligand is illustrated by the preparation of complexes with three different metals: rhodium, iridium and nickel. The rhodium and iridium complexes contained the [MCl(COD] fragments, while the nickel compound contained [NiCpCl]. The preparation of the tris-MIC (MIC = mesoionic carbene complex with three [IrCl(CO2] fragments, allowed the estimation of the Tolman electronic parameter (TEP for the ligand, which was compared with the TEP value for a related 1,3,5-triphenylbenzene-tris-NHC ligand. The electronic properties of the tris-MIC ligand were studied by cyclic voltammetry measurements. In all cases, the tris-MIC ligand showed a stronger electron-donating character than the corresponding NHC-based ligands. The catalytic activity of the tri-rhodium complex was tested in the addition reaction of arylboronic acids to α,β-unsaturated ketones.

  8. Enhancing effects of salt formation on catalytic activity and enantioselectivity for asymmetric hydrogenation of isoquinolinium salts by dinuclear halide-bridged iridium complexes bearing chiral diphosphine ligands. (United States)

    Kita, Yusuke; Yamaji, Kenta; Higashida, Kosuke; Sathaiah, Kandula; Iimuro, Atuhiro; Mashima, Kazushi


    Asymmetric hydrogenation of 1- and 3-substituted and 1,3-disubstituted isoquinolinium chlorides using triply halide-bridged dinuclear iridium complexes [{Ir(H)(diphosphine)}2 (μ-Cl)3 ]Cl has been achieved by the strategy of HCl salt formation of isoquinolines to afford the corresponding chiral 1,2,3,4-tetrahydroisoquinolines (THIQs) in high yields and with excellent enantioselectivities after simple basic work-up. The effects of salt formation have been investigated by time-course experiments, which revealed that the generation of isoquinolinium chlorides clearly prevented formation of the catalytically inactive dinuclear trihydride complex, which was readily generated in the catalytic reduction of salt-free isoquinoline substrates. Based on mechanistic investigations, including by (1) H and (31) P{(1) H} NMR studies and the isolation and characterization of several intermediates, the function of the chloride anion of the isoquinolinium chlorides has been elucidated, allowing us to propose a new outer-sphere mechanism involving coordination of the chloride anion of the substrates to an iridium dihydride species along with a hydrogen bond between the chloride ligand and the N-H proton of the substrate salt. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. High-dose rate iridium-192 brachytherapy with flexible applicator. A trial toward decrease of stress during treatment and improvement of quality of life

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Keiji; Kasahara, Kotaro; Karashima, Takashi; Inoue, Yuichiro; Kariya, Shinji; Inomata, Taisuke; Yoshida, Shoji; Shuin, Taro [Kochi Medical School, Nankoku (Japan)


    We tried to improve the materials and methods of high-dose rate Iridium-192 brachytherapy for localized prostate cancer and evaluated the stress during the treatment in 20 patients with whom the therapy was performed. Rigid applicators made of stainless steel of 1.6 mm in diameter were indwelt with a template as usual for 30 hours in 14 patients (group A). Flexible applicators made of polyoxymethylene rosin (POM) of 2.0 mm in diameter were indwelt without a template for 30 hours after the applicator insertion in 6 patients (group B). We made inquiries about lumbago, inconvenience and necessity of assistant help and sleep in the course of therapy, and urinary incontinence and erectile function after the course of therapy as the QOL. The stress during the course of therapy in the patients of group B was obviously less than that of group A. There were no significant differences in urinary incontinence and erectile function after the course of therapy between group A and B. In this study, our trial successfully reduced the stress during the course of therapy in the patients with localized prostate cancer in the course of high-dose rate Iridium-192 brachytherapy. (author)

  10. Iridium(I) complexes with anionic N-heterocyclic carbene ligands as catalysts for the hydrogenation of alkenes in nonpolar media. (United States)

    Kolychev, Eugene L; Kronig, Sabrina; Brandhorst, Kai; Freytag, Matthias; Jones, Peter G; Tamm, Matthias


    A series of lithium complexes of anionic N-heterocyclic carbenes that contain a weakly coordinating borate moiety (WCA-NHC) was prepared in one step from free N-heterocyclic carbenes by deprotonation with n-butyl lithium followed by borane addition. The reaction of the resulting lithium-carbene adducts with [M(COD)Cl]2 (M = Rh, Ir; COD = 1,5-cyclooctadiene) afforded zwitterionic rhodium(I) and iridium(I) complexes of the type [(WCA-NHC)M(COD)], in which the metal atoms exhibit an intramolecular interaction with the N-aryl groups of the carbene ligands. For M = Rh, the neutral complex [(WCA-NHC)Rh(CO)2] and the ate complex (NEt4)[(WCA-NHC)Rh(CO)2Cl] were prepared, with the latter allowing an assessment of the donor ability of the ligand by IR spectroscopy. The zwitterionic iridium-COD complexes were tested as catalysts for the homogeneous hydrogenation of alkenes, which can be performed in the presence of nonpolar solvents or in the neat alkene substrate. Thereby, the most active complex showed excellent stability and activity in hydrogenation of alkenes at low catalyst loadings (down to 10 ppm).

  11. Highly efficient and concentration-insensitive organic light-emitting devices based on self-quenching-resistant orange–red iridium complex

    Energy Technology Data Exchange (ETDEWEB)

    Qi, Yige; Wang, Xu [State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Optoelectronic Information, University of Electronic Science and Technology of China (UESTC), Chengdu 610054 (China); Li, Ming [College of Chemistry, Sichuan University, Chengdu 610064 (China); Lu, Zhiyun, E-mail: [College of Chemistry, Sichuan University, Chengdu 610064 (China); Yu, Junsheng, E-mail: [State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Optoelectronic Information, University of Electronic Science and Technology of China (UESTC), Chengdu 610054 (China)


    Orange–red phosphorescent organic light-emitting devices (PHOLEDs) with high efficiency and concentration insensitivity based on a novel iridium complex, bis[2-(biphenyl-4-yl)benzothiazole-N,C{sup 2}′]iridium(III) (acetylacetonate) [(4Phbt){sub 2}Ir(acac)], were fabricated. With the heavily doped emissive layer (EML) of 4,4′-N,N′-dicarbazolylbiphenyl (CBP): (4Phbt){sub 2}Ir(acac) in a wide and easily controlled dopant concentration range from 12 wt% to 24 wt%, a maximum power efficiency of 29 lm/W and an external quantum efficiency of >16% of the PHOLEDs were obtained, implying the insensitivity of electroluminescence (EL) properties to doping concentration. Meanwhile, a maximum power efficiency of 5.0 lm/W was achieved from a non-doped device with neat (4Phbt){sub 2}Ir(acac) as the EML, indicating a superior property of self-quenching resistance. The mechanism of direct exciton formation, in which exciton-formation regions are distributed throughout the EML, is responsible for the significant alleviation of triplet–triplet annihilation and superior EL performance. - Highlights: • Highly efficient and concentration-insensitive PHOLEDs were obtained. • The high efficiency of non-doped PHOLEDs indicated a quenching-resistant property. • The independence of EL spectra on doping concentration was observed. • The heavily doped devices were dominated by mechanism of direct exciton formation.

  12. Preparation and determination of kerma for Iridium 192 sources of low dose rate for brachytherapy; Preparacion y determinacion del kerma de fuentes de iridio-192 de baja tasa de dosis para braquiterapia

    Energy Technology Data Exchange (ETDEWEB)

    Tendilla, J.I.; Tovar M, V.; Mitsoura, E.; Aguilar H, F.; Alanis M, J. [Instituto Nacional de Investigaciones Nucleares, C.P. 52045-1, Salazar, Esrado de Mexico, D.F. (Mexico)


    The practice of Brachytherapy with Iridium-192 sources of low dose rate (0.4 - 0.8 Gy/h) is a technique used in the treatment of diverse illnesses. in this work the preparation, quality control and calibration are presented in terms of kerma in air of Iridium-192 using as target these recycled Iridium-Platinum wires. The targets were obtained as decayed sources of different radio therapeutical centers in the country and they were characterized by Scanning electron microscopy in order to determine their chemical composition. Subsequently it was developed an experimental design to establish the effect of neutron flux, geometrical array and irradiation time over the activity and percentage of the sources homogeneity. The homogeneity was determined by auto radiography and by Gamma spectroscopy. Once the optimal irradiation conditions were established, it is determined the apparent activity and kerma in air using a well type ionization chamber with traceability to a primary laboratory. Iridium-192 sources were obtained with an average homogeneity 96 %, apparent activity 282.129 {+-} 0.531 M Bq and kerma in air 0.03200 {+-} 0.00006 m Gy m/h A. (Author)

  13. A relativistic DFT methodology for calculating the structures and NMR chemical shifts of octahedral platinum and iridium complexes. (United States)

    Vícha, Jan; Patzschke, Michael; Marek, Radek


    A methodology for optimizing the geometry and calculating the NMR shielding constants is calibrated for octahedral complexes of Pt(IV) and Ir(III) with modified nucleic acid bases. The performance of seven different functionals (BLYP, B3LYP, BHLYP, BP86, TPSS, PBE, and PBE0) in optimizing the geometry of transition-metal complexes is evaluated using supramolecular clusters derived from X-ray data. The effects of the size of the basis set (ranging from SVP to QZVPP) and the dispersion correction (D3) on the interatomic distances are analyzed. When structural deviations and computational demands are employed as criteria for evaluating the optimizations of these clusters, the PBE0/def2-TZVPP/D3 approach provides excellent results. In the next step, the PBE0/def2-TZVPP approach is used with the continuum-like screening model (COSMO) to optimize the geometry of single molecules for the subsequent calculation of the NMR shielding constants in solution. The two-component zeroth-order regular approximation (SO-ZORA) is used to calculate the NMR shielding constants (PBE0/TZP/COSMO). The amount of exact exchange in the PBE0 functional is validated for the nuclear magnetic shieldings of atoms in the vicinity of heavy transition metals. For the PBE0/TZP/COSMO setup, an exact exchange of 40% is found to accurately reproduce the experimental NMR shielding constants for both types of complexes. Finally, the effect of the amount of exact exchange on the NMR shielding calculations (which is capable of compensating for the structural deficiencies) is analyzed for various molecular geometries (SCS-MP2, BHLYP, and PBE0) and the influence of a trans-substituent on the NMR chemical shift of nitrogen is discussed. The observed dependencies for an iridium complex cannot be rationalized by visualizing the Fermi-contact (FC) induced spin density and probably originate from changes in the d-d transitions that modulate the spin-orbit (SO) part of the SO/FC term.

  14. Heteroleptic cyclometalated iridium(III) complexes displaying blue phosphorescence in solution and solid state at room temperature. (United States)

    Yang, Cheng-Han; Li, Shih-Wen; Chi, Yun; Cheng, Yi-Ming; Yeh, Yu-Shan; Chou, Pi-Tai; Lee, Gene-Hsiang; Wang, Chih-Hsiang; Shu, Ching-Fong


    A series of heteroleptic Ir(III) metal complexes 1-3 bearing two N-phenyl-substituted pyrazoles and one 2-pyridyl pyrazole (or triazole) ligands were synthesized and characterized to attain highly efficient, room-temperature blue phosphorescence. The N-phenylpyrazole ligands, dfpzH = 1-(2,4-difluorophenyl)pyrazole, fpzH = 1-(4-fluorophenyl)pyrazole, dfmpzH = 1-(2,4-difluorophenyl)-3,5-dimethylpyrazole, and fmpzH = 1-(4-fluorophenyl)-3,5-dimethylpyrazole, show a similar reaction pattern with respect to the typical cyclometalated (C(wedge)N) chelate, which utilizes its ortho-substituted phenyl segment to link with the central Ir(III) atom, while the second 2-pyridylpyrazole (or triazole) ligand, namely, fppzH = 3-(trifluoromethyl)-5-(2-pyridyl)pyrazole, fptzH = 3-(trifluoromethyl)-5-(2-pyridyl)triazole, and hptzH = 3-(heptafluoropropyl)-5-(2-pyridyl)triazole, undergoes typical anionic (N--N) chelation to complete the octahedral framework. X-ray structural analyses on complexes [(dfpz)(2)Ir(fppz)] (1a) and [(fmpz)(2)Ir(hptz)] (3d) were established to confirm their molecular structures. Increases of the pipi energy gaps of the Ir(III) metal complexes were systematically achieved with two tuning strategies. One involves the substitution for one or two fluorine atoms at the N-phenyl segment or the introduction of two electron-releasing methyl substituents at the pyrazole segment of the H(C--N) ligands. Alternatively, we have applied the more electron-accepting triazolate in place of the pyrazolate segment for the third (N--N)H ligand. Our results, on the basis of steady-state, relaxation dynamics, and theoretical approaches, lead to a conclusion that, for complexes 1-3, the weakening of iridium metal-ligand bonding strength in the T(1) state plays a crucial role for the fast radiationless deactivation. For the case of [(fmpz)(2)Ir(hptz)] (3d), a thermal deactivation barrier of 4.8 kcal/mol was further deduced via temperature-dependent studies. The results provide a

  15. Effect of the substituents on the photophysical, electrochemical and electroluminescence properties of OLED dopant Iridium bis(2-phenylbenzothiozolato- N,C2')(acetylacetonate) (United States)

    Ivanov, P.; Tomova, R.; Petrova, P.


    The effect of two substituents: clorine and 1,3-diphenylpropane-1,3-dionate, placed on different position in the molecule of Iridium (III) bis(2-phenylbenzothiozolato-N,C2')- (acetylacetonate) (bt)2Ir(acac), on its electrochemical behaviour, photophysical and electroluminescence properties were investigated. Three complexes (bt)2Ir(acac), Iridium (III) bis[2-(4-chlorophenyl)benzothiazolato-N,C2']-acetylacetonate (Clbt)2Ir(acac), in which the Cl atom was introduced on the 4-position in the benzothiazole ring, and the new Iridium (Ill) bis[2 -phenylbenzothiazolato -N,C2'] -(1,3 -diphenylpropane-1,3 -dionate) (bt)2Ir(dbm), where ancillary acetylacetonate ligand was replaced by 1,3-diphenylpropane-1,3-dionate, were synthesized and characterised by 1H-NMR and elemental analysis. The HOMO/LUMO energy levels of the complexes were determined by cyclic voltammetry (CV) and their properties were established by UV-Visible and fluorescence spectroscopy. The application of (Clbt)2Ir(acac), (bt)2Ir(bsm) and (bt)2Ir(acac) as dopants in hole transporting layer (HTL) of Organic light- emitting diodes(OLEDs). It was found that with respect to the reference (bt)2Ir(acac): both LUMO and HOMO of the substituted complexes were shifted to more positive values accordingly with 0.23 and 0.19 eV for (Clbt)2Ir(acac) and 0.14 and 0.12 eV for (bt)2Ir(dbm). OLEDs doped with 1 w% of the complexes irradiated the warm white light with Commission internationale de l'eclairage (CIE) coordinates: 0.24;0.38 for (Clbt)2Ir(acac), 0.30;0.44 for (bt)2Ir(acac) and 0.28;0.46 for (bt)2Ir(dbm). Devices doped with 10 w% of all complexes irradiated in the yellow orange region of the spectrum.

  16. Bis(o-methylserotonin)-containing iridium(III) and ruthenium(II) complexes as new cellular imaging dyes: synthesis, applications, and photophysical and computational studies. (United States)

    Núñez, Cristina; Silva López, Carlos; Faza, Olalla Nieto; Fernández-Lodeiro, Javier; Diniz, Mario; Bastida, Rufina; Capelo, Jose Luis; Lodeiro, Carlos


    We report the synthesis, characterization, and scope of a new versatile emissive molecular probe functionalized with a 1,10-phenanthroline moiety containing methylserotonin groups as binding sites for metal ion recognition. The synthesis, characterization, and evaluation of the in vitro imaging capability of the iridium(III) and ruthenium(II) complexes [Ir(ppy)2(N-N)](+) and [Ru(bpy)2(N-N)](2+), in which ppy is 2-phenylpyridine, bpy is 2,2'-bipyridine, and N-N is a 1,10-phenanthroline ligand functionalized with two methylserotonin groups to serve as binding sites for metal ion recognition, is reported. The uptake of these compounds by living freshwater fish (Carassius auratus) was studied by fluorescence microscopy, and the cytotoxicity of ligand N-N and [Ru(bpy)2(N-N)](2+) in this species was also investigated.

  17. Reversible hydrogen storage using CO2 and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures. (United States)

    Hull, Jonathan F; Himeda, Yuichiro; Wang, Wan-Hui; Hashiguchi, Brian; Periana, Roy; Szalda, David J; Muckerman, James T; Fujita, Etsuko


    Green plants convert CO(2) to sugar for energy storage via photosynthesis. We report a novel catalyst that uses CO(2) and hydrogen to store energy in formic acid. Using a homogeneous iridium catalyst with a proton-responsive ligand, we show the first reversible and recyclable hydrogen storage system that operates under mild conditions using CO(2), formate and formic acid. This system is energy-efficient and green because it operates near ambient conditions, uses water as a solvent, produces high-pressure CO-free hydrogen, and uses pH to control hydrogen production or consumption. The extraordinary and switchable catalytic activity is attributed to the multifunctional ligand, which acts as a proton-relay and strong π-donor, and is rationalized by theoretical and experimental studies.

  18. Thermal expansion, heat capacity and Grüneisen parameter of iridium phosphide Ir2P from quasi-harmonic Debye model (United States)

    Liu, Z. J.; Song, T.; Sun, X. W.; Ma, Q.; Wang, T.; Guo, Y.


    Thermal expansion coefficient, heat capacity, and Grüneisen parameter of iridium phosphide Ir2P are reported by means of quasi-harmonic Debye model for the first time in the current study. This model combines with first-principles calculations within generalized gradient approximation using pseudopotentials and a plane-wave basis in the framework of density functional theory, and it takes into account the phononic effects within the quasi-harmonic approximation. The Debye temperature as a function of volume, the Grüneisen parameter, thermal expansion coefficient, constant-volume and constant-pressure heat capacities, and entropy on the temperature T are also successfully obtained. All the thermodynamic properties of Ir2P in the whole pressure range from 0 to 100 GPa and temperature range from 0 to 3000 K are summarized and discussed in detail.

  19. Transformation of 1,3-imidazolidine-2-thione (SC ₃H ₆N ₂2) into (SC ₃H ₄N ₄–O–N ₂C ₃H ₄S) ² ⁻ dianion chelated in [Pd{κ ³–S, O, S–(SC ₃H ₄N ₂–O–N ₂C ₃H ₄S)}(PPh₃)]•CH₃CN

    Indian Academy of Sciences (India)



    Reaction of [PdCl ₂ (PPh ₃) ₂] with imidazolidine-2-thione {SC₃H₄ (NH) ₂} in the presence of triethylamineinvolved activation of N–H bonds and formed an unusual oxo-bridged dianion, (SC ₃H ₄N ₄–O–N ₂C ₃H ₄S) ² ⁻ coordinated to PdII in [Pd{κ ³–S, O,S–(SC ₃H ₄N ₂–O–N ₂C ₃H ₄S)}(PPh₃)]•CH₃CN 1, which hasbeen studied using elemental analysis, IR, NMR, X-ray crystallography and ESI-mass studies.

  20. Effects of cathodic current density and temperature on morphology and microstructure of iridium coating prepared by electrodeposition in molten salt under the air atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Zhu Li' an, E-mail: [Department of Materials Engineering and Applied Chemistry, College of Aerospace and Materials Engineering, National University of Defence Technology, Changsha 410073 (China); Bai Shuxin; Zhang Hong; Ye Yicong [Department of Materials Engineering and Applied Chemistry, College of Aerospace and Materials Engineering, National University of Defence Technology, Changsha 410073 (China)


    Highlights: Black-Right-Pointing-Pointer The 'salt passivation' occurs on the anode surface at low temperatures. Black-Right-Pointing-Pointer The index of preferred growth crystal plane increases as increasing current density. Black-Right-Pointing-Pointer The <1 1 1> oriented coating is smoother and denser than <2 2 0>/<3 1 1> oriented coating. Black-Right-Pointing-Pointer The coating compactness improves as increasing current density/decreasing temperature. - Abstract: Iridium coating was prepared on a Re/C substrate (graphite substrate coated with rhenium coating by CVD) using electrodeposition in molten salt of chlorides in the air atmosphere. The effects of cathodic current density and temperature on both the morphology and microstructure of the coating were studied, respectively. The morphology and orientation of the coating were determined by scanning electron microscope and X-ray diffraction, respectively. The results showed that the cathodic current density and temperature both affected the surface morphology, roughness, grain size and compactness of the iridium coating. With increasing of current density from 5 to 50 mA/cm{sup 2}, the surface roughness of the coating increased from Ra 0.98 to Ra 6.29 {mu}m, while the grain size decreased. With temperature increasing from 520 to 640 Degree-Sign C, the surface roughness of the coating decreased from Ra 4.41 to Ra 1.16 {mu}m, while the grain size increased. The preferred orientations of the coatings changed in the row <111>-<220>-<311> with current density increasing. With the increase of temperature, the preferred orientation of the coating changed from <1 1 1> to <2 2 0>, and again to <1 1 1>. The coating with <1 1 1> orientation was smoother and denser than that with <2 2 0> orientation regardless of the grain size.

  1. Carbon isotope curve and iridium anomaly in the Albian-Cenomanian paleoceanic deposits of the Eastern Kamchatka (United States)

    Savelyev, D. P.; Savelyeva, O. L.; Palechek, T. N.; Pokrovsky, B. G.


    determined contents of carbon and oxygen stable isotopes in limestones and have compared the received results to isotope curves of other regions. In studied section the curve of d13C is characterized by a clearly expressed positive shift at the level of the lower carbonaceous bed. Below it and in the overlapping stratum of siliceous limestone (1 cm thickness) d13C has the values of 1.9-2.1 pro mille and above it d13C increases up to 2.5-3 pro mille. The precise d13C maximum after a sharp shift is correlatable with the form of a d13C curve of the Middle Cenomanian Tethyan sections. Accordingly, it is possible to assert, that the lower carbonaceous bed was formed during the mid-Cenomanian anoxic event (MCE). Gradual increase of d13C in the upper part of our section is similar to change of d13C in Upper Cenomanian fragments of Tethyan sections, i.e. the lower carbonaceous bed corresponds to anoxic event at the Cenomanian/Turonian boundary (OAE2). Neutron activation analysis indicates increased up to 9 ppb concentration of Ir at the bottom of the lower carbonaceous bed (inorganic part of the sample was analyzed comprising 46% of the bulk rock). This anomaly correlates in the studied section with a positive shift of d13C. Taking into account radiolarian age data this allows to correlate the anomaly with the MCE. A source of iridium and other elements of the platinum group could be basalts and hyaloclastites from the eruptions during the sedimentation period. Anoxic conditions promoted deposit enrichment in ore elements. This work was supported by the RFBR (No. 10-05-00065).

  2. Crystal structures of fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) monohydrate and fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) methanol hemisolvate: rhodium structures that are isotypic with their iridium analogs. (United States)

    Merola, Joseph S; Franks, Marion A


    The crystal structures of two solvates of fac-tri-chlorido-tris-(tri-methyl-phosphane-κP)rhodium(III) are reported, i.e. one with water in the crystal lattice, fac-[RhCl3(Me3P)3]·H2O, and one with methanol in the crystal lattice, fac-[RhCl3(Me3P)3]·0.5CH3OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al. (2013 ▶). Polyhedron, 54, 67-73]. Comparison is made between the rhodium and iridium compounds, highlighting their isostructural relationships.

  3. Investigation on the Electrochemiluminescence Properties of a Series of Cyclometalated Iridium(Ill) Complexes Based on 2-Phenylquinoline Derivatives%系列2-苯基喹啉类铱配合物的合成及电化学发光性能研究

    Institute of Scientific and Technical Information of China (English)

    童碧海; 梅群波; 李志文; 董永平; 张千峰


    以4-甲氧羰基-2-苯基喹啉为环金属配体,NAN辅助配体为解离配体合成了一系列离子型环金属铱配合物.配合物的结构通过质谱、核磁进行了表征.配合物1还测试了其单晶结构.对配合物的紫外、磷光性质进行了表征,溶液状态下为红光发射,波长在610-620nm之间,磷光寿命在133-496ns之间,量子效率在0.7%-16.6%.铱配合物的电化学发光与Ru(bpy)32+有所不同,发光电位比Ru(bpy)2+要高,且大部分铱配合物在正负电位都能发光,最大发光强度是Ru(bpy)3^2+的三倍.%A series of cyclometalated iridium(III) complexes ([Ir(pqcm)2(bpy)][PF6] (1), [Ir(pqcm)2(dafo)[PF6] (2), [Ir(pqcm)z(phen)][PF6] (3), [Ir(pqcm)2(altpy)][PF6] (4), [Ir(pqcm)z(bbim)][PF6] (5), [Ir(pqcm)2(bvbbim)][PF6] (6), pqcm= 2-phenyl-quinoline-4-carboxylic acid methyl ester, bpy=2,2'-bipyridine, dafo----4,5-diazafluoren-9-one, phen----1,10- phenanthroline, altpy = 4'-allyloxy-2,2':6',2"-terpyridine, bbim ---- 2,2'-bibenzimidazole, bvbbim ---- 1,1'-diallyl-2,2'-bibenz- imidazole) were synthesized with cyclometalated ligand of pqcm and NAN typical assistant ligands. New iridium(III) com- plexes were characterized by the NMR and mass spectroscopies, and the single crystal structure of complex 1 was measured, the cationic distorted octahedrally coordinated iridium(III) center was ligated by two cyclometalated pqcm ligands and one chelating bpy ligand with a negative [PF6] counter anion. In CH2C12 solution, the iridium(III) complexes 1, 2 and 3 dis- played orange red emissions with wavelength about 610 nm, while the iridium(III) complexes 4, 5 and 6 displayed pure red emissions with wavelength about 620 rim, which was desirable for example in organic light-emitting devices applications. The iridium(III) complexes had lifetimes between 133 ns and 496 ns, quantum efficiencies between 0.7% and 16.6%. All these iridium(III) complexes had higher quantum

  4. Satellite Collision Modeling with Physics-Based Hydrocodes: Debris Generation Predictions of the Iridium-Cosmos Collision Event and Other Impact Events

    Energy Technology Data Exchange (ETDEWEB)

    Springer, H K; Miller, W O; Levatin, J L; Pertica, A J; Olivier, S S


    Satellite collision debris poses risks to existing space assets and future space missions. Predictive models of debris generated from these hypervelocity collisions are critical for developing accurate space situational awareness tools and effective mitigation strategies. Hypervelocity collisions involve complex phenomenon that spans several time- and length-scales. We have developed a satellite collision debris modeling approach consisting of a Lagrangian hydrocode enriched with smooth particle hydrodynamics (SPH), advanced material failure models, detailed satellite mesh models, and massively parallel computers. These computational studies enable us to investigate the influence of satellite center-of-mass (CM) overlap and orientation, relative velocity, and material composition on the size, velocity, and material type distributions of collision debris. We have applied our debris modeling capability to the recent Iridium 33-Cosmos 2251 collision event. While the relative velocity was well understood in this event, the degree of satellite CM overlap and orientation was ill-defined. In our simulations, we varied the collision CM overlap and orientation of the satellites from nearly maximum overlap to partial overlap on the outermost extents of the satellites (i.e, solar panels and gravity boom). As expected, we found that with increased satellite overlap, the overall debris cloud mass and momentum (transfer) increases, the average debris size decreases, and the debris velocity increases. The largest predicted debris can also provide insight into which satellite components were further removed from the impact location. A significant fraction of the momentum transfer is imparted to the smallest debris (< 1-5mm, dependent on mesh resolution), especially in large CM overlap simulations. While the inclusion of the smallest debris is critical to enforcing mass and momentum conservation in hydrocode simulations, there seems to be relatively little interest in their

  5. Relations Between Stabilities and Structures of Closo Borane Dianions

    Institute of Scientific and Technical Information of China (English)

    LI Ping


    An effective method to investigate the stabilities of a series of new closo-BnHn2-(n = 12, 14, 16, 18, 20, 22, 24, 30) was put forward with the aid of G96PW91/SHC calculations. Stabilities are related to the relative stabilized energies (RSE) and the 2e3c bound geometries of closo-BnHn2-. The structures in which a boron atom connects to four atoms up to seven are stable and appear in many borides because of the lower relative stabilized energy. In geometries, both triangular and quadrangular faces are in favor of forming the structures of closo-BnHn2-. The energies of optimized geometries support the existence of these new compounds. By employing both RSE and ▲E per boron atom in cage, the stabilities were studied to predict the probabilities of unknown clusters in existence. The electron-deficient clusters can be understood that the positive holes should be disperse to every triangular face and lead to share the holes, wherever there are not enough electrons to occupy them. The negative charges which anions carry distribute to 2e3c bonds to increase the stabilities.

  6. Ultraviolet Spectroscopy of Metal-Poor Stars: New Detections of Phosphorus, Germanium, Arsenic, Selenium, Cadmium, Tellurium, Lutetium, Osmium, Iridium, Platinum, Gold, and More! (United States)

    Roederer, Ian U.


    Ultraviolet spectroscopy with HST/STIS provides a 30% increase in the number of elements that can be detected in metal-poor stars. Although nearly every element from hydrogen through bismuth is probably present in most metal-poor stars, not all elements can be detected. The resonance lines of the dominant species of some elements are only found in the UV in late-type stars. The chemical compositions of these stars reflect the history of stellar nucleosynthesis from the first stars to today. Here, I present a summary of recent work that has expanded the chemical inventory in metal-poor stars using UV spectroscopy conducted using HST/STIS. The highlights include new detections of phosphorus, germanium, arsenic, selenium, cadmium, tellurium, lutetium, osmium, iridium, platinum, and gold in metal-poor stars. These detections reveal new insights into stellar nucleosynthesis in the earliest generations of massive stars, provide new constraints on the r-process, and open new channels for chemically-tagging stars that have assembled to form the Milky Way stellar halo.

  7. Iridium(III) and Rhodium(III) compounds of dipyridyl-N-alkylimine and dipyridyl-NH-ketimine: Spectral characterization and crystal structure

    Indian Academy of Sciences (India)



    Pentamethylcyclopentadienyl iridium(III) and rhodium(III) complexes of formulation [(η⁵- C₅Me₅)M{(C₅H₄N) ₂C=NR)}Cl]PF₆ were prepared by the reaction of [MCl2(η⁵-C₅Me₅)] ₂ (M = Ir or Rh) with dipyridyl-N-alkylimine ligands, (C₅H₄N) ₂C=NR (R = Me or Et) in the presence of NH₄PF₆ at room temperature. The reaction also produced an unexpected dipyridyl-NH-ketimine organometallic compound [(η⁵-C₅Me₅)M {(C₅H₄N) ₂C=NH}Cl]PF6 as minor product when the reaction was performed under refluxing acetonitrile. The NH-ketimine compounds were formed via N-C single bond cleavage of imine ligand resulting in coordination of the transformed ligand, (C5₅H₄N) ₂C=NH to the metal centre. Complexes were obtained as their hexafluorophosphate salts and characterized based on IR, NMR and ESI-MS spectroscopic data. Authenticity of NH-ketimine organometallic compound was established by single crystal X-ray analysis of a representative compound, which crystallized in orthorhombic space group Pbcn and has a pseudo-octahedral geometry around the metal ion.

  8. The Photoluminescent Properties of New Cationic Iridium(III Complexes Using Different Anions and Their Applications in White Light-Emitting Diodes

    Directory of Open Access Journals (Sweden)

    Hui Yang


    Full Text Available Three cationic iridium(III complexes [Ir(ppy2(phen][PF6] (C1, [Ir(ppy2(phen]2SiF6 (C2 and [Ir(ppy2(phen]2TiF6 (C3 (ppy: 2-phenylpyridine, phen: 1, 10-phenanthroline using different anions were synthesized and characterized by 1H Nuclear magnetic resonance (1HNMR, mass spectra (MS, Fourier transform infrared (FTIR spectra and element analysis (EA. After the ultraviolet visible (UV-vis absorption spectra, photoluminescent (PL properties and thermal properties of the complexes were investigated, complex C1 and C3 with good optical properties and high thermal stability were used in white light-emitting diodes (WLEDs as luminescence conversion materials by incorporation with 460 nm-emitting blue GaN chips. The integrative performances of the WLEDs fabricated with complex C1 and C3 are better than those fabricated with the widely used yellow phosphor Y3Al5O12:Ce3+ (YAG. The color rendering indexes of the WLEDs with C1 and C3 are 82.0 and 82.6, the color temperatures of them are 5912 K and 3717 K, and the maximum power efficiencies of them are 10.61 Lm·W−1 and 11.41 Lm·W−1, respectively.

  9. Kinetics of the chemical oxidation of (5,10,15,20-tetraphenyl-21H,23H-porphinato)(chloro)(aqua)iridium(III) (United States)

    Tyulyaeva, E. Yu.; Bichan, N. G.; Mozhzhukhina, E. G.; Lomova, T. N.


    The oxidation of (Cl)(H2O)IrTPP with atmospheric oxygen in the presence of concentrated H2SO4 accompanied by coordination of molecular O2 and substitution of axial ligands was studied spectrophotometrically. In 16.785-18.09 MH2SO4 at 298-318 K, (Cl)(H2O)IrTPP experienced two single-electron oxidations in sequence: with an increase in the oxidation state of the iridium cation and with formation of the π-radical cation form (HSO4)IrIVTPP•+ oxidized at the aromatic ligand ( k 298 = 7.2 × 10-6 mol-1 L s-1). Referring to the literature data on the oxidation of (Cl)(H2O)IrTPP in AcOH and CF3COOH, it was shown that the medium acidity and the nature of the axial ligands affect the electron removal site in the chemical oxidation of (Cl)(H2O)IrTPP with atmospheric oxygen in proton-donor solvents.

  10. Efficient catalytic interconversion between NADH and NAD+ accompanied by generation and consumption of hydrogen with a water-soluble iridium complex at ambient pressure and temperature. (United States)

    Maenaka, Yuta; Suenobu, Tomoyoshi; Fukuzumi, Shunichi


    Regioselective hydrogenation of the oxidized form of β-nicotinamide adenine dinucleotide (NAD(+)) to the reduced form (NADH) with hydrogen (H(2)) has successfully been achieved in the presence of a catalytic amount of a [C,N] cyclometalated organoiridium complex [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(H(2)O)](2) SO(4) [1](2)·SO(4) under an atmospheric pressure of H(2) at room temperature in weakly basic water. The structure of the corresponding benzoate complex Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))-benzoate-κC(3))(H(2)O) 2 has been revealed by X-ray single-crystal structure analysis. The corresponding iridium hydride complex formed under an atmospheric pressure of H(2) undergoes the 1,4-selective hydrogenation of NAD(+) to form 1,4-NADH. On the other hand, in weakly acidic water the complex 1 was found to catalyze the hydrogen evolution from NADH to produce NAD(+) without photoirradiation at room temperature. NAD(+) exhibited an inhibitory behavior in both catalytic hydrogenation of NAD(+) with H(2) and H(2) evolution from NADH due to the binding of NAD(+) to the catalyst. The overall catalytic mechanism of interconversion between NADH and NAD(+) accompanied by generation and consumption of H(2) was revealed on the basis of the kinetic analysis and detection of the catalytic intermediates.

  11. Iridium ultrasmall nanoparticles, worm-like chain nanowires, and porous nanodendrites: One-pot solvothermal synthesis and catalytic CO oxidation activity (United States)

    Zhang, Tao; Li, Shuai-Chen; Zhu, Wei; Ke, Jun; Yu, Jing-Wen; Zhang, Zhi-Ping; Dai, Lin-Xiu; Gu, Jun; Zhang, Ya-Wen


    We report a facile one-pot solvothermal synthesis of monodisperse iridium (Ir) ultrasmall (1.5-2.5 nm in diameter) nanoparticles (NPs), worm-like chain nanowires (NWs), and porous nanodendrites (NDs), for which CO oxidation reaction has been employed as a probe reaction to investigate the effects of nanoparticle size and surface-capping organics on the catalytic activities. Time-dependent experiments revealed that an oriented attachment mechanism induced by the strong adsorption of halide anions (Br- and I-) on specific facet of Ir nanoclusters or by decreasing the reduction rate of Ir precursors with changing their concentrations during the synthesis was responsible for the formation of Ir NWs and NDs. Annealing tests indicated that an O2-H2 atmosphere treatment turned out to be an effective measure to clean up the surface-capping organics of Ir NPs supported on commercial SiO2. Catalytic CO oxidation reaction illustrated that a significant improvement in the catalytic activity of CO oxidation reaction was achieved together with the changing of activation energies after such atmosphere treatment for the supported catalysts of the ultrasmall Ir NPs. It is noteworthy that this enhancement in catalytic activity could be ascribed to the changes in the surface status (including populations of Ir species in metallic and oxidized states, removal of surface capping organics, the variety of active sites, and total effective active site number) for the supported nanocatalysts during the atmosphere treatment.

  12. Composition-dependent electrocatalytic activity of palladium-iridium binary alloy nanoparticles supported on the multiwalled carbon nanotubes for the electro-oxidation of formic acid. (United States)

    Bao, Jianming; Dou, Meiling; Liu, Haijing; Wang, Feng; Liu, Jingjun; Li, Zhilin; Ji, Jing


    Surface-functionalized multiwalled carbon nanotubes (MWCNTs) supported Pd100-xIrx binary alloy nanoparticles (Pd100-xIrx/MWCNT) with tunable Pd/Ir atomic ratios were synthesized by a thermolytic process at varied ratios of bis(acetylacetonate) palladium(II) and iridium(III) 2,4-pentanedionate precursors and then applied as the electrocatalyst for the formic acid electro-oxidation. The X-ray diffraction pattern (XRD) and transmission electron microscope (TEM) analysis showed that the Pd100-xIrx alloy nanoparticles with the average size of 6.2 nm were uniformly dispersed on the MWCNTs and exhibited a single solid solution phase with a face-centered cubic structure. The electrocatalytic properties were evaluated through the cyclic voltammetry and chronoamperometry tests, and the results indicated that both the activity and stability of Pd100-xIrx/MWCNT were strongly dependent on the Pd/Ir atomic ratios: the best electrocatalytic performance in terms of onset potential, current density, and stability against CO poisoning was obtained for the Pd79Ir21/MWCNT. Moreover, compared with pure Pd nanoparticles supported on MWCNTs (Pd/MWCNT), the Pd79Ir21/MWCNT exhibited enhanced steady-state current density and higher stability, as well as maintained excellent electrocatalytic activity in high concentrated formic acid solution, which was attributed to the bifunctional effect through alloying Pd with transition metal.

  13. Synthesis, Characterization, Properties and DFT Calculations of 2-(Benzo[b]thiophen-2-yl)pyridine-based Iridium(III) Complexes with Different Ancillary Ligands. (United States)

    Li, Gao-Nan; Zeng, Yong-Pi; Li, Kai-Xiu; Chen, Hao-Hua; Xie, Hui; Zhang, Fu-Lin; Chen, Guang-Ying; Niu, Zhi-Gang


    A series of new cyclometalated btp-based iridium(III) complexes with three different ancillary ligands, Ir(btp)2(bozp) (3a), Ir(btp)2(btzp) (3b) and Ir(btp)2(izp) (3c) (btp = 2-(benzo[b]thiophen-2-yl)pyridine, bozp =2-(benzo[d]oxazol-2-yl)phenol, btzp =2-(benzo[d]thiazol-2-yl)phenol, izp = 2-(2 H-indazol-2-yl)phenol), have been synthesized and fully characterized. The crystal structure of 3b has been determined by single crystal X-ray diffraction analysis. A comparative study has been carried out for complexes 3a - 3c by UV-vis absorption spectroscopy, photoluminescence spectroscopy, cyclic voltammetry and DFT calculations. This observation illustrates that the substitution of N or S in ancillary ligand can lead to a marked bathochromic shift of absorption and emission wavelengths. The spectroscopic characterisation of these complexes has been complemented by DFT and TD-DFT calculations, supporting the assignment of (3)MLCT/(3)LC to the lowest energy excited state.

  14. Isomerization of Internal Alkynes to Iridium(III Allene Complexes via C–H Bond Activation: Expanded Substrate Scope, and Progress towards a Catalytic Methodology

    Directory of Open Access Journals (Sweden)

    Neha Phadke


    Full Text Available The synthesis of a series of allene complexes (POCOPIr(η2-RC=.=CR’ 1b–4b (POCOP = 2,6-bis(di-tert-butylphosphonitobenzene via isomerization of internal alkynes is reported. We have demonstrated that the application of this methodology is viable for the isomerization of a wide variety of alkyne substrates. Deuterium labeling experiments support our proposed mechanism. The structures of the allene complexes 1b–4b were determined using spectroscopic data analysis. Additionally, the solid-state molecular structure of complex 2b was determined using single crystal X-ray diffraction studies and it confirmed the assignment of an iridium-bound allene isomerization product. The rates of isomerization were measured using NMR techniques over a range of temperatures to allow determination of thermodynamic parameters. Finally, we report a preliminary step towards developing a catalytic methodology; the allene may be liberated from the metal center by exposure of the complex to an atmosphere of carbon monoxide.

  15. Theoretical characterization of quaternary iridium based hydrides NaAeIrH{sub 6} (Ae = Ca, Ba and Sr)

    Energy Technology Data Exchange (ETDEWEB)

    Bouras, S. [Laboratory of Studies Surfaces and Interfaces of Solids Materials, Department of Physics, Faculty of Science, University of Setif 1, 19000 (Algeria); Ghebouli, B., E-mail: [Laboratory of Studies Surfaces and Interfaces of Solids Materials, Department of Physics, Faculty of Science, University of Setif 1, 19000 (Algeria); Benkerri, M. [Laboratory of Studies Surfaces and Interfaces of Solids Materials, Department of Physics, Faculty of Science, University of Setif 1, 19000 (Algeria); Ghebouli, M.A., E-mail: [Microelectronic Laboratory (LMSE), University of Bachir Ibrahimi, Bordj-Bou-Arreridj 34000 (Algeria); Research Unit on Emerging Materials (RUEM), University of Setif 1, 19000 (Algeria); Choutri, H. [Microelectronic Laboratory (LMSE), University of Bachir Ibrahimi, Bordj-Bou-Arreridj 34000 (Algeria); Louail, L.; Chihi, T.; Fatmi, M. [Research Unit on Emerging Materials (RUEM), University of Setif 1, 19000 (Algeria); Bouhemadou, A. [Laboratory for Developing New Materials and Their Characterization, Department of Physics, Faculty of Science, University of Setif 1, 19000 (Algeria); Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451 (Saudi Arabia); Khenata, R.; Khachai, H. [Laboratoire de Physique Quantique et de Modélisation Mathématique, Université de Mascara, 29000 (Algeria)


    The quaternary iridium based hydrides NaAeIrH{sub 6} (Ae = Ca, Ba and Sr) are promising candidates as hydrogen storage materials. We have studied the structural, elastic, electronic, optical and thermodynamic properties of NaAeIrH{sub 6} (Ae = Ca, Ba and Sr) within the generalized gradient approximation, the local density approximation (LDA) and mBj in the frame of density functional perturbation theory. These alloys have a large indirect Γ–X band gap. The thermodynamic functions were computed using the phonon density of states. The origin of the possible transitions from valence band to conduction band was illustrated. By using the complex dielectric function, the optical properties such as absorption, reflectivity, loss function, refractive index and optical conductivity have been obtained. - Graphical abstract: Real and imaginary parts of the dielectric function, the absorption spectrum α(ω), reflectivity R(ω) and energy-loss spectrum L(ω). - Highlights: • NaAeIrH{sub 6} (Ae = Ca, Ba and Sr) alloys have been investigated. • The elastic moduli, energy gaps are predicted. • The optical and thermal properties were studied.

  16. Ratiometric Molecular Probes Based on Dual Emission of a Blue Fluorescent Coumarin and a Red Phosphorescent Cationic Iridium(III) Complex for Intracellular Oxygen Sensing. (United States)

    Yoshihara, Toshitada; Murayama, Saori; Tobita, Seiji


    Ratiometric molecular probes RP1 and RP2 consisting of a blue fluorescent coumarin and a red phosphorescent cationic iridium complex connected by a tetra- or octaproline linker, respectively, were designed and synthesized for sensing oxygen levels in living cells. These probes exhibited dual emission with good spectral separation in acetonitrile. The photorelaxation processes, including intramolecular energy transfer, were revealed by emission quantum yield and lifetime measurements. The ratios (R(I) = (I(p)/I(f))) between the phosphorescence (I(p)) and fluorescence (I(f)) intensities showed excellent oxygen responses; the ratio of R(I) under degassed and aerated conditions ( R(I)(0) was 20.3 and 19.6 for RP1 and RP2. The introduction of the cationic Ir (III) complex improved the cellular uptake efficiency compared to that of a neutral analogue with a tetraproline linker. The emission spectra of the ratiometric probes internalized into living HeLa or MCF-7 cells could be obtained using a conventional microplate reader. The complex RP2 with an octaproline linker provided ratios comparable to the ratiometric measurements obtained using a microplate reader: the ratio of the R(I)) value of RP2 under hypoxia (2.5% O2) to that under normoxia (21% O2) was 1.5 and 1.7 for HeLa and MCF-7 cells, respectively. Thus, the intracellular oxygen levels of MCF-7 cells could be imaged by ratiometric emission measurements using the complex RP2.

  17. White organic light-emitting devices based on fac tris(2-phenylpyridine) iridium sensitized 5,6,11,12-tetraphenylnap-hthacene

    Institute of Scientific and Technical Information of China (English)

    DING Gui-ying; WANG Jin; JIANG Wen-long; WANG Jing; WANG Li-zhong; CHANG XI


    We have fabricated the white organic light-emitting devices (WOLEDs) based on 4,4'-bis(2,2-diphenyl vinyl)-1,1'-biphenyl (DPVBi) and phosphorescence sensitized 5,6,11,12,-tetraphenylnaphthacene (rubrene).The device structure is ITO/2T-NATA (20 nm)/NPBX (20 nm)/CBP:x%Ir(ppy)3:0.5% rubrene (8 nm)/NPBX (5 nm)/DPVBi (30 nm)/Alq(30nm)/LiF(0.5 nm)/Al.In the devices,DPVBi acts as a blue light-emitting layer,the rubrene is sensitized by a phosphorescent material,fac tris (2-phenylpyridine) iridium [Ir(ppy)3],acts as a yellow light-emitting layer,and N,N'-bis-(1-naphthyl)-N,N'-dipheny1-1,1'-biphenyl-4,4'-diamine (NPBX) acts as a hole transporting and exciton blocker layer,respectively.When the concentration of Ir(PPY)3 is 6wt%,the maximum luminance is 24960 cd/m2 at an applied voltage of 15 V,and the maximum luminous efficiency is 5.17 cd/A at an applied voltage of 8 V.

  18. Iridium oxides based gate interface of AlGaN/GaN high electron mobility transistors formed by high temperature oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Lalinský, T. [Institute of Electrical Engineering of the Slovak Academy of Sciences, Dúbravská cesta 9, 841 04 Bratislava (Slovakia); Vallo, M., E-mail: [Institute of Electrical Engineering of the Slovak Academy of Sciences, Dúbravská cesta 9, 841 04 Bratislava (Slovakia); Vanko, G.; Dobročka, E. [Institute of Electrical Engineering of the Slovak Academy of Sciences, Dúbravská cesta 9, 841 04 Bratislava (Slovakia); Vincze, A. [International Laser Centre, Ilkovičova 3, 841 04 Bratislava (Slovakia); Osvald, J.; Rýger, I.; Dzuba, J. [Institute of Electrical Engineering of the Slovak Academy of Sciences, Dúbravská cesta 9, 841 04 Bratislava (Slovakia)


    We report on a high temperature forming of iridium oxides (IrO{sub 2}) gates of circular AlGaN/GaN high electron mobility transistors (C-HEMTs) to be predetermined for high temperature applications. IrO{sub 2} gate interfacial layer is formed by high temperature oxidation (T = 500–800 °C, for 1 min) of 15 nm thick Ir gate contact layer. A comprehensive microstructural and electrical characterization of the IrO{sub 2} gates is carried out to explain the improved transport properties and thermal stability of the gate interfaces. It is found that the transformation of Ir gate layer into its crystalline IrO{sub 2} phase at oxidation temperatures of 700 °C and 800 °C provides the high barrier gate interface with prevailing thermionic emission transport mechanism. Accelerated reliability tests are used to confirm C-HEMT thermally stable performance deduced from both the gate interface and 2DEG channel stability. The introduced AlGaN/GaN C-HEMTs with high temperature grown IrO{sub 2} gates seem to be very attractive for both the high temperature operated electronic and sensor devices.

  19. Photoredox radical conjugate addition of dithiane-2-carboxylate promoted by an iridium(iii) phenyl-tetrazole complex: a formal radical methylation of Michael acceptors. (United States)

    Gualandi, Andrea; Matteucci, Elia; Monti, Filippo; Baschieri, Andrea; Armaroli, Nicola; Sambri, Letizia; Cozzi, Pier Giorgio


    A readily accessible iridium(iii) phenyl-tetrazole complex ([Ir(ptrz)2(tBu-bpy)](+), 2; Hptrz = 2-methyl-5-phenyl-tetrazole; tBu-bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) is shown to be a versatile catalyst for a new photocatalytic Michael reaction. Under light irradiation in the presence of 2, a dithiane 2-carboxylic acid, obtained by simple hydrolysis of a commercially available ethyl ester, generates a 1,3-dithiane radical capable of performing addition to a variety of Michael acceptors (e.g., unsaturated ketones, esters, amides and malonates). This broad scope reaction with high yields is a formal photo-redox addition of the elusive methyl radical and the adducts obtained can be starting materials for a variety of functionalized products. The excited-state oxidation potential of catalyst 2 allows selective formation of radicals only from α-heterosubstituted carboxylates. Chemical modification of this metal complex can tune the electrochemical properties, opening a route to new highly selective catalytic photo-oxidation reactions.

  20. Eletrodeposição de irídio em tubo de grafite como modificador químico permanente em espectrometria de absorção atômica Electrodeposition of iridium in graphite tube as permanent chemical modifier in atomic absorption spectrometry

    Directory of Open Access Journals (Sweden)

    Juliana Naozuka


    Full Text Available A tubular electrochemical flow-cell for iridium deposition on the inner surface of pyrolytic graphite tube for permanent chemical modification is proposed. A transversal heated graphite tube was used as working electrode, a cylindrical piece of graphite inserted into the graphite tube as auxiliary electrode, and a micro Ag/AgCl(sat as reference electrode. Iridium solution in 1.0 mol L-1 HCl, flowing at 0.55 mL min-1 for 60 min was used to perform the electrochemical modification. The applied potential to the flow-cell was - 0.700 V vs Ag/AgCl. Scanning electron microscopy images were taken for thermal and electrochemical modified graphite surface in order to evaluate the iridium distribution. Selenium hydride trapping was used to verify the performance of the proposed permanent chemical modifier.

  1. Formation and reactivity of a porphyrin iridium hydride in water: acid dissociation constants and equilibrium thermodynamics relevant to Ir-H, Ir-OH, and Ir-CH2- bond dissociation energetics. (United States)

    Bhagan, Salome; Wayland, Bradford B


    Aqueous solutions of group nine metal(III) (M = Co, Rh, Ir) complexes of tetra(3,5-disulfonatomesityl)porphyrin [(TMPS)M(III)] form an equilibrium distribution of aquo and hydroxo complexes ([(TMPS)M(III)(D(2)O)(2-n)(OD)(n)]((7+n)-)). Evaluation of acid dissociation constants for coordinated water show that the extent of proton dissociation from water increases regularly on moving down the group from cobalt to iridium, which is consistent with the expected order of increasing metal-ligand bond strengths. Aqueous (D(2)O) solutions of [(TMPS)Ir(III)(D(2)O)(2)](7-) react with dihydrogen to form an iridium hydride complex ([(TMPS)Ir-D(D(2)O)](8-)) with an acid dissociation constant of 1.8(0.5) × 10(-12) (298 K), which is much smaller than the Rh-D derivative (4.3 (0.4) × 10(-8)), reflecting a stronger Ir-D bond. The iridium hydride complex adds with ethene and acetaldehyde to form organometallic derivatives [(TMPS)Ir-CH(2)CH(2)D(D(2)O)](8-) and [(TMPS)Ir-CH(OD)CH(3)(D(2)O)](8-). Only a six-coordinate carbonyl complex [(TMPS)Ir-D(CO)](8-) is observed for reaction of the Ir-D with CO (P(CO) = 0.2-2.0 atm), which contrasts with the (TMPS)Rh-D analog which reacts with CO to produce an equilibrium with a rhodium formyl complex ([(TMPS)Rh-CDO(D(2)O)](8-)). Reactivity studies and equilibrium thermodynamic measurements were used to discuss the relative M-X bond energetics (M = Rh, Ir; X = H, OH, and CH(2)-) and the thermodynamically favorable oxidative addition of water with the (TMPS)Ir(II) derivatives.

  2. Synthesis, structure, and reactivity of rhodium and iridium complexes of the chelating bis-sulfoxide tBuSOC2H4SOtBu. Selective O-H activation of 2-hydroxy-isopropyl-pyridine. (United States)

    Schaub, Thomas; Diskin-Posner, Yael; Radius, Udo; Milstein, David


    The chloro-bridged rhodium and iridium complexes [M2(BTSE)2Cl2] (M = Rh 1, Ir 2) bearing the chelating bis-sulfoxide tBuSOC2H4SOtBu (BTSE) were prepared by the reaction of [M2(COE)4Cl2] (M = Rh, Ir; COE = cyclooctene) with an excess of a racemic mixture of the ligand. The cationic compounds [M(BTSE)2][PF6] (M = Rh 3, Ir 4), bearing one S- and one O-bonded sulfoxide, were also obtained in good yields. The chloro-bridges in 2 can be cleaved with 2-methyl-6-pyridinemethanol and 2-aminomethyl pyridine, resulting in the iridium(I) complexes [Ir(BTSE)(Py)(Cl)] (Py = 2-methyl-6-pyridinemethanol 5, 2-aminomethyl-pyridine 6). In case of the bulky 2-hydroxy- isopropyl-pyridine, selective OH oxidative addition took place, forming the Ir(III)-hydride [Ir(BTSE)(2-isopropoxy-pyridine)(H)(Cl)] 7, with no competition from the six properly oriented C-H bonds. The cationic rhodium(I) and iridium(I) compounds [M(BTSE)(2-aminomethyl-pyridine)][X] (M = Rh 8, Ir 10), [Rh(BTSE)(2-hydroxy- isopropyl-pyridine)][X] 9(stabilized by intramolecular hydrogen bonding), [Ir(BTSE)(pyridine)2][PF6] 12, [Ir(BTSE)(alpha-picoline)2][PF6] 13, and [Rh(BTSE)(1,10-phenanthroline)][PF6] 14 were prepared either by chloride abstraction from the dimeric precursors or by replacement of the labile oxygen bonded sulfoxide in 3 or 4. Complex 14 exhibits a dimeric structure in the solid state by pi-pi stacking of the phenanthroline ligands.

  3. W、Mo、Re基体熔盐电沉积Ir涂层初探%Preliminary Study on Iridium Coatings Electrodeposited on Mo,W and Re Substrates in Molten Salts

    Institute of Scientific and Technical Information of China (English)

    仝永刚; 白书欣; 张虹; 陈柯; 朱利安; 李顺


    采用熔盐电沉积法在W、Mo、Re基体表面分别制备了Ir涂层,通过扫描电镜和能谱分析了涂层的形貌和成分,对比研究了W、Mo、Re在熔盐电沉积Ir涂层过程中的性质。结果表明:W和Mo在氯化物熔盐体系中腐蚀严重,电沉积后在基体和涂层之间形成了含有腐蚀产物的夹盐层,大大降低了涂层和基体之间的结合力,在热应力和外力的作用下涂层易产生裂纹和剥落。Re在氯化物熔盐体系中稳定性好,在氯化物熔盐体系中不发生腐蚀,电沉积后在基体和涂层之间无夹盐层形成,基体和涂层结合良好,电沉积所得Ir涂层致密、完整,没有裂纹和孔洞等缺陷。%The iridium coatings were prepared on the surfaces of molybdenum,tungsten and rhenium substrates by electrodeposition in molten salts of chlorides.The microstructures,compositions and phase constituents of the coatings were investigated by scanning electron microscopy(SEM) and energy-dispersive X-ray spectrometry(EDX).Characteristics of molybdenum,tungsten and rhenium substrates during electrodeposition were studied.The results indicated that molybdenum and tungsten were severely corroded in molten salts of chlorides,interlayers composed of chlorides and corrosion products were formed after electrodeposition,which greatly reduced the binding force between the coating and substrate,and the iridium coatings fractured easily.However,rhenium has a good stabilization in chlorides.No corrosion was found during electrodeposition,there is no interlayer formed,and the iridium coating and rhenium substrate immediately combined,a dense and smooth iridium coating was obtained on the rhenium substrate.

  4. DFT/TDDFT investigation on the electronic structures and photophysical properties of phosphorescent iridium(III) complexes with 2-(pyridin-2-yl)-benzo[d]imidazole ligand

    Energy Technology Data Exchange (ETDEWEB)

    Shang, Xiaohong, E-mail: [College of Chemistry and Life Science, Changchun University of Technology, Changchun 130012 (China); Han, Deming [School of Life Science and Technology, Changchun University of Science and Technology, Changchun 130022 (China); Li, Dongfeng [College of Chemistry and Life Science, Changchun University of Technology, Changchun 130012 (China); Zhang, Gang [State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023 (China)


    We have reported a theoretical analysis of a series of heteroleptic iridium(III) complexes (mpmi){sub 2}Ir(pybi) [mpmi=1-(4-tolyl)-3-methyl-imidazole, pybi=2-(pyridin-2-yl)-benzo[d]imidazole] (1a), (fpmi){sub 2}Ir(pybi) [fpmi=1-(4-fluoro-phenyl)-3-methyl-imidazole] (1b), (tfpmi){sub 2}Ir(pybi) [tfpmi=1-methyl-3-(4-trifluoromethyl-phenyl)-imidazole] (1c), (pypmi){sub 2}Ir(pybi) [pypmi=3-(3-methyl-imidazol)-pyrazole] (2a), (phpymi){sub 2}Ir(pybi) [phpymi=3-(3-methyl-imidazol)-5-phenyl-pyrazole] (2b), and (inpymi){sub 2}Ir(pybi) [inpymi=3-(3-methyl-imidazol)-indeno[1,2-c]pyrazole] (2c) by using the density functional theory (DFT) method to investigate their electronic structures and photophysical properties and obtain further insights into the phosphorescent efficiency mechanism. By changing cyclometalated ligands, the conjugation length, and substituents of the cyclometalated ligands, one can tune the emission color from green (λ{sub em}=520 nm) to orange (λ{sub em}=592 nm). Complexes 1a, 1b, 2a, and 2b have the almost identical emission wavelength about 550 nm, while 592 nm for 1c and 520 nm for 2c are red shifted and blue shifted, respectively, relative to 1a. The calculated results indicate that, for 1b and 1c, the substituents of −F and −CF{sub 3} at the phenyl moiety cause a poor hole-injection ability compared with that of 1a. For all these complexes studied, the hole-transporting performances are better than the electron-transporting ones. The difference between reorganization energies for hole transport (λ{sub ih}) and reorganization energies for electron transport (λ{sub ie}) for complex 1c are relatively smaller, indicating that the hole and electron transfer balance could be achieved more easily in the emitting layer. The alteration of cyclometalated ligands with different conjugation lengths and substituents has an impact on the optoelectronic properties of these complexes. It is believed that the larger metal to ligand charge transfer (MLCT

  5. Impact of Substituents on Excited-State and Photosensitizing Properties in Cationic Iridium(III) Complexes with Ligands of Coumarin 6. (United States)

    Takizawa, Shin-Ya; Ikuta, Naoya; Zeng, Fanyang; Komaru, Shohei; Sebata, Shinogu; Murata, Shigeru


    A series of bis-cyclometalated cationic iridium (Ir) complexes were synthesized employing two coumarin 6 ligands and a 2,2'-bipyridine (bpy) with various substituents as new sensitizers, realizing both features of strong visible-light absorption and long-lived excited state. Complexes 2-4, with electron-donating methyl and methoxy groups, absorbed visible light strongly (ε: 126 000-132 000 M(-1) cm(-1)) and exhibited room-temperature phosphorescence with remarkably long lifetimes (21-23 μs) in dichloromethane. In contrast, the excited state of prototype complex 1 without any substituents was short-lived, particularly in highly polar acetonitrile. Phosphorescence of complex 5 with the strong electron-withdrawing CF3 groups was too weak to be detected at room temperature even in less polar dichloromethane. The triplet energies of their coumarin ligand-centered ((3)LC) phosphorescent states were almost invariable, demonstrating that selective tuning of the excited-state lifetime is possible through this "simple chemical modification of the bpy ligand" (we name it the "SCMB" method). The spectroscopic and computational investigations in this study suggest that a potential source of the nonradiative deactivation is a triplet ligand-to-ligand charge-transfer state ((3)LLCT state, coumarin 6 → bpy) and lead us to conclude that the energy level of this dark (3)LLCT state, as well as its thermal population, is largely dependent on the substituents and solvent polarity. In addition, the significant difference in excited-state lifetime was reflected in the photosensitizing ability of complexes 1-5 in visible-light-driven hydrogen generation using sodium ascorbate and a cobalt(III) diglyoxime complex as an electron donor and a water-reduction catalyst, respectively. This study suggests that the SCMB method should be generally effective in controlling the excited state of other bis-cyclometalated cationic Ir(III) complexes.

  6. White polymer light-emitting diodes co-doped with three phosphorescent iridium(III) complexes aimed at improvement of color rendering properties

    Energy Technology Data Exchange (ETDEWEB)

    Ikawa, Shigeru [Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531 (Japan); Yagi, Shigeyuki, E-mail: [Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531 (Japan); Maeda, Takeshi; Nakazumi, Hiroyuki [Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531 (Japan); Sakurai, Yoshiaki [Textile and Polymer Section, Technology Research Institute of Osaka Prefecture, 2-7-1 Ayumino, Izumi, Osaka 594-1157 (Japan)


    To obtain white electroluminescence (EL) with a high color rendering index (CRI), we fabricated polymer light-emitting diodes (PLEDs) co-doped with high-efficiency blue-, yellow- and red-phosphorescent bis-cyclometalated iridium(III) complexes (Ir-1, Ir-2, and Ir-3, respectively) in a single emitting layer based on a PVCz-OXD-7 blended film (PVCz, poly(9-vinylcarbazole); OXD-7, 1,3-bis[5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene). When the constituent ratio of the emitting layer (PVCz:OXD-7:Ir-1:Ir-2:Ir-3) was adjusted to 10:3.0:1.2:0.060:0.036 in weight ratio, an approximately white PLED (WPLED) was obtained showing a Commission Internationale de l'Eclairage (CIE) chromaticity coordinate of (0.38, 0.44) and a CRI of 83 at 1000 cd m{sup −2}. To elucidate the energy transfer among the phosphorescent emitters, we also investigated the photophysical properties of the PVCz-based thin film whose constituent ratio is the same as the emitting layer of the WPLED, and it was found that a cascade of the energy transfer from the blue to the red via the yellow emitter considerably contributes to the emission process along with the direct energy transfer from the blue to the red and yellow emitters. - Highlights: • PLEDs co-doped with three phosphorescent emitters were fabricated. • Approximately white EL with a color rendering index of 83 was obtained. • The energy transfer mechanism among the phosphorescent emitters was elucidated.

  7. On-particle detection of Plasmodium falciparum histidine-rich protein II by a "switch-on" iridium(III) probe. (United States)

    Davis, Keersten M; Bitting, Anna L; Wright, David W


    The need for robust reagents for biomarker detection has become an increasing necessity in designing point-of-care diagnostics. We report a non-emissive, cyclometalated iridium(III) complex, Ir(ppy)2(H2O)2(+) (Ir1), which, on coordination to a histidine-containing protein bound to the surface of a magnetic particle, elicits a rapid, long-lived phosphorescent signal. The interactions between Ir1 and numerous other amino acids were examined for activity, but only the addition of histidine resulted in a four orders of magnitude enhancement in signal intensity. Buffer conditions (pH and temperature) and composition (coordinating vs. non-coordinating and ionic strength) were optimized to achieve maximum signal and stability of Ir1. The activity of the probe under optimized conditions was validated with BNT-II, a histidine-containing branched peptide mimic of the malarial biomarker Plasmodium falciparum histidine-rich protein II (PfHRPII). By comparing Ir1 binding to BNT-II versus L-histidine, steric and quenching effects were noted in the peptide. Despite these deviations from ideal conditions, signal response reached saturation with both BNT-II and recombinant HRPII (rcHRPII). When immobilized on the surface of a 50 μM magnetic agarose particles, the limit of detection of rcHRPII was 14.5 nM. The robust signal response of this inorganic probe lends itself to future applications in on-particle enzyme-linked immunosorbent assay (ELISA)-based assays.

  8. Discovery of unique and ENM- specific pathophysiologic pathways: Comparison of the translocation of inhaled iridium nanoparticles from nasal epithelium versus alveolar epithelium towards the brain of rats. (United States)

    Kreyling, Wolfgang G


    The biokinetics of inhaled nanoparticles (NP) is more complex than that of larger particles since NP may NP deposited on the nasal mucosa of the upper respiratory tract (URT) may translocate to the olfactory bulb of the brain and also via the trigeminus (URT neuronal route); and (b) NP deposited in the lower respiratory tract (LRT) may cross the ABB into blood and enter the brain across the blood-brain-barrier (BBB) or take a neuronal route from enervated tracheo-bronchial epithelia via the vagus nerve. Translocation from both - the URT and the LRT - are quantified during the first 24h after a 1-hour aerosol inhalation of 20nm-sized, (192)Ir radiolabeled iridium NP by healthy adult rats using differential exposures: (I) nose-only exposure of the entire respiratory tract or (II) intratracheal (IT) inhalation of intubated and ventilated rats, thereby bypassing the URT and extrathoracic nasal passages. After nose-only exposure brain accumulation (BrAcc) is significantly nine-fold higher than after IT inhalation since the former results from both pathways (a+b) while the latter exposure comes only from pathway (b). Interestingly, there are significantly more circulating NP in blood 24h after nose-only inhalation than after IT inhalation. Distinguishing translocation from URT versus LRT estimated from the differential inhalation exposures, the former is significantly higher (8-fold) than from the LRT. Although the BrAcc fraction is rather low compared to total NP deposition after this short-term exposure, this study proofs that inhaled insoluble NP can accumulate in the brain from both - URT and LRT which may trigger and/or modulate adverse health effects in the central nervous system (CNS) during chronic exposure.

  9. The labeling of unsaturated γ-hydroxybutyric acid by heavy isotopes of hydrogen: iridium complex-mediated H/D exchange by C─H bond activation vs reduction by boro-deuterides/tritides. (United States)

    Marek, Aleš; Pedersen, Martin H F; Vogensen, Stine B; Clausen, Rasmus P; Frølund, Bente; Elbert, Tomáš


    3-Hydroxycyclopent-1-ene-1-carboxylic acid (HOCPCA (1)) is a potent ligand for high-affinity γ-hydroxybutyric acid binding sites in the central nervous system. Various approaches to the introduction of a hydrogen label onto the HOCPCA skeleton are reported. The outcomes of the feasible C─H activation of olefin carbon (C-2) by iridium catalyst are compared with the reduction of the carbonyl group (C-3) by freshly prepared borodeuterides. The most efficient iridium catalysts proved to be Kerr bulky phosphine N-heterocyclic species providing outstanding deuterium enrichment (up to 91%) in a short period of time. The highest deuterium enrichment (>99%) was achieved through the reduction of ketone precursor 2 by lithium trimethoxyborodeuteride. Hence, analogical conditions were used for the tritiation experiment. [(3) H]-HOCPCA selectively labeled on the position C-3 was synthetized with radiochemical purity >99%, an isolated yield of 637 mCi and specific activity = 28.9 Ci/mmol.

  10. Accelerated partial breast irradiation with iridium-192 multicatheter PDR/HDR brachytherapy. Preliminary results of the German-Austrian multicenter trial

    Energy Technology Data Exchange (ETDEWEB)

    Ott, O.J.; Lotter, M.; Sauer, R.; Strnad, V. [Dept. of Radiation Oncology, Univ. Hospital Erlangen, Erlangen (Germany); Poetter, R.; Resch, A. [Dept. of Radiotherapy and Radiobiology, Univ. Hospital AKH Wien, Vienna (Austria); Hammer, J. [Dept. of Radiation Oncology, Barmherzige Schwestern Hospital Linz, Linz (Austria); Hildebrandt, G. [Dept. of Radiation Oncology, Univ. Hospital Leipzig, Leipzig (Germany); Poehls, U.; Beckmann, M.W. [Dept. of Gynecology, Univ. Hospital Erlangen, Erlangen (Germany)


    : this analysis indicates that accelerated partial breast irradiation with iridium-192 interstitial multicatheter PDR/HDR implants is feasible with low perioperative morbidity, low acute and mild late toxicity, and does not significantly affect cosmetic results at a median follow-up of 24 months. (orig.)

  11. The influence of hydrogen peroxide and histamine on lung permeability and translocation of iridium nanoparticles in the isolated perfused rat lung

    Directory of Open Access Journals (Sweden)

    Takenaka Shinji


    Full Text Available Abstract Background Translocation of ultrafine particles (UFP into the blood that returns from the lungs to the heart has been forwarded as a mechanism for particle-induced cardiovascular effects. The objective of this study was to evaluate the role of the endothelial barrier in the translocation of inhaled UFP from the lung into circulation. Methods The isolated perfused rat lung (IPRL was used under negative pressure ventilation, and radioactive iridium particles (18 nm, CMD, 192Ir-UFP were inhaled during 60 minutes to achieve a lung burden of 100 – 200 μg. Particle inhalation was done under following treatments: i control perfusion, ii histamine (1 μM in perfusate, iii luminal histamine instillation (1 mM, and iv luminal instillation of H2O2. Particle translocation to the perfusate was assessed by the radioactivity of 192Ir isotope. Lung permeability by the use of Tc99m-labeled diethylene triamine pentaacetic acid (DTPA. In addition to light microscopic morphological evaluation of fixed lungs, alkaline phosphatase (AKP and angiotensin converting enzyme (ACE in perfusate were measured to assess epithelial and endothelial integrity. Results Particle distribution in the lung was homogenous and similar to in vivo conditions. No translocation of Ir particles at negative pressure inhalation was detected in control IPL, but lungs pretreated with histamine (1 μM in the perfusate or with luminal H2O2 (0.5 mM showed small amounts of radioactivity (2–3 % dose in the single pass perfusate starting at 60 min of perfusion. Although the kinetics of particle translocation were different from permeability for 99mTc-DTPA, the pretreatments (H2O2, vascular histamine caused similar changes in the translocation of particles and soluble mediator. Increased translocation through epithelium and endothelium with a lag time of one hour occurred in the absence of epithelial and endothelial damage. Conclusion Permeability of the lung barrier to UFP or

  12. 新型铱配合物磷光材料的合成及性质研究%Synthesis and Characterization of Novel Iridium Complex Phosphorescent Materials

    Institute of Scientific and Technical Information of China (English)

    刘芃; 俞天智; 牛丽霞; 康俊丹; 梁瑞芝; 史彦龙; 张成成


    两个含有载流子β-二酮配体的新型铱配合物被成功合成。分别为Ir(L)2(acac-Ox)和Ir(L)2(acac-Cz)。其中L=3-(2-吡啶)香豆素环金属铱配合物, acac-Ox=3-(4-(5-(4'-叔丁基苯基)-1,3,4-噁二唑)苄基)-戊二酮, acac-Cz=3-((4-(9-咔唑-)苯基)甲基)戊烷-2,4-戊二酮,并且通过了核磁,紫外等数据分析。配合物的光物理性质采用紫外-可见,光致发光光谱分析研究。配合物acac-Cz做成的器件,在9%的参杂浓度下器件的发光效率效果最佳。配合物acac-Ox当参杂浓度为6%时,器件的发光效率最佳。通过对器件发光性能的比较, acac-Cz通过引入咔唑空穴传输基团提高了器件的性能。它们都是很好的绿光发光材料。%Two new iridium complexes containing carrier β-diketone ligands were successfully synthesized , namely Ir(L)2(acac-Ox) and Ir(L)2(acac-Cz), in which L=3-(pyridin-2-yl)coumarinatoringmetaliridiumcomplexes , acac-Ox=3-(4-(5-(4′-tertbutylphenyl) -1,3,4-oxadiazole)benzyl) -pentane-2,4-dionateandacac -Cz=3-((4 -(9H -carbazol -9 -yl) phenyl) methyl) pentane -2,4 -dionate, and were successfully synthesized and characterized by elemental analysis , 1 H NMR and FT-IR.Photophysical properties of complexes using UV -visible , photoluminescence spectroscopy were studied.The devices based on Ir ( L ) 2 ( acac -Cz ) with 9%(ω) doping concentration showed the best EL efficiency performance , and emits green light.The devices based on Ir(L)2(acac-Ox) with 6%(ω) doping concentration showed the best EL efficiency performance acac -Cz by introducing a carbazolyl group to improve the hole transport properties of the device.

  13. Synthesis, structural, spectral, thermal and antimicrobial studies of palladium(II), platinum(II), ruthenium(III) and iridium(III) complexes derived from N,N,N,N-tetradentate macrocyclic ligand. (United States)

    Rani, Soni; Kumar, Sumit; Chandra, Sulekh


    Palladium(II), platinum(II), ruthenium(III) and iridium(III) complexes of general stoichiometry [PdL]Cl(2), [PtL]Cl(2), [Ru(L)Cl(2)]Cl and [Ir(L)Cl(2)]Cl are synthesized with a tetradentate macrocyclic ligand, derived from 2,6-diaminopyridine with 3-ethyl 2,4-pentanedione. Ligand was characterized on the basis of elemental analyses, IR, mass, and (1)H NMR and (13)C NMR spectral studies. All the complexes were characterized by elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, mass, electronic spectral techniques and thermal studies. The value of magnetic moments indicates that all the complexes are diamagnetic except Ru(III) complex which shows magnetic moments corresponding its one unpaired electron. The macrocyclic ligand and all its metal complexes were also evaluated in vitro against some plant pathogenic fungi and bacteria to assess their biocidal properties.

  14. A rapid and practical strategy for the determination of platinum, palladium, ruthenium, rhodium, iridium and gold in large amounts of ultrabasic rock by inductively coupled plasma optical emission spectrometry combined with ultrasound extraction (United States)

    Zhang, Gai; Tian, Min


    This proposed method regulated the determination of platinum, palladium, ruthenium, rhodium, iridium and gold in platinum-group ores by nickel sulfide fire assay—inductively coupled plasma optical emission spectrometry (ICP-OES) combined with ultrasound extraction for the first time. The quantitative limits were 0.013-0.023μg/g. The samples were fused to separate the platinum-group elements from matrix. The nickel sulfide button was then dissolved with hydrochloric acid and the insoluble platinum-group sulfide residue was dissolved with aqua regia by ultrasound bath and finally determined by ICP-OES. The proposed method has been applied into the determination of platinum-group element and gold in large amounts of ultrabasic rocks from the Great Dyke of Zimbabwe.

  15. 2-(Methylamido)pyridine-Borane: A Tripod κ(3)-N,H,H Ligand in Trigonal Bipyramidal Rhodium(I) and Iridium(I) Complexes with an Asymmetric Coordination of Its BH3 Group. (United States)

    Brugos, Javier; Cabeza, Javier A; García-Álvarez, Pablo; Kennedy, Alan R; Pérez-Carreño, Enrique; Van der Maelen, Juan F


    The complexes [M(κ(3)-N,H,H-mapyBH3)(cod)] (M = Rh, Ir; HmapyBH3 = 2-(methylamino)pyridine-borane; cod = 1,5-cyclooctadiene), which contain a novel anionic tripod ligand coordinated to the metal atom through the amido N atom and through two H atoms of the BH3 group, were prepared by treating the corresponding [M2(μ-Cl)2(cod)2] (M = Rh, Ir) precursor with K[mapyBH3]. X-ray diffraction studies and a theoretical Quantum Theory of Atoms in Molecules analysis of their electron density confirmed that the metal atoms of both complexes are in a very distorted trigonal bipyramidal coordination environment, in which two equatorial sites are asymmetrically spanned by the H-B-H fragment. While both 3c-2e BH-M interactions are more κ(1)-H (terminal σ coordination of the B-H bond) than κ(2)-H,B (agostic-type coordination of the B-H bond), one BH-M interaction is more agostic than the other, and this difference is more marked in the iridium complex than in the rhodium one. This asymmetry is not evident in solution, where the cod ligand and the BH3 group of these molecules participate in two concurrent dynamic processes of low activation energies (variable-temperature NMR and density functional theory studies), namely, a rotation of the cod ligand that interchanges its two alkene fragments (through a square pyramidal transition state) and a rotation of the BH3 group about the B-N bond that equilibrates the three B-H bonds (through a square planar transition state). While the cod rotation has similar activation energy in 2 and 3, the barrier to the BH3 group rotation is higher in the iridium complex than in the rhodium one.

  16. Electrochemiluminescence of Two Iridium(Ⅲ)Complexes%铱配合物的电致化学发光性能研究

    Institute of Scientific and Technical Information of China (English)

    魏巧华; 韩李静; 段亚男; 肖方南; 陈裕松; 张兰; 陈国南


    It has been attracted great attention to develop new and high efficient electrochemiluminescent (ECL) reagents for increasing the application of ECL. The ECL studies on two complexes [Ir(ppy)2L] (PF6 ) ( ppy = 2-phenylpyridine, L1 = ( 4-[2 , 2'] bipyridinyl-5ylethynylphenyl) pyridin-2ylmethylthiophen-2ylmethylamine; L2 = ( 4-[ 2, 2'] bipyridinyl-5ylethynylphenyl ) bispyridin2-ylmethylamine) have been performed in this study. It was found that the ECL intensity peaks of two iridium (Ⅲ) complexes at glassy carbon working electrode with tri-n-propyl-amine(TPrA) as coreactant appeared at potential of 1.52 and 1.32 V, and the maxima ECL emission centered at 620- 640 nm. The ECL intensity was well linear with the concentration of [Ir(ppy)2L1] (PF6) and [Ir(ppy)2L2] (PF6) in the range of 2 × 10-7 - 1.6 × 10- 6 moI/L and 2 r 10-8 - 2 × 10-6 mol/L, respectively. In addition, at the same condition, the ECL intensity of the [Ir(ppy) 2L2] (PF6)/TPrA system was higher than that of [Ir( ppy) 2L1] ( PF6)/TPrA system, and was identical to that of [Ru(bpy) 3 ] 2+ /TPrA system.%结构相关的铱配合物[Ir(ppy)2L1](PF6)和[Ir(ppy)2L2](PF6)(ppy=2-苯基吡啶,LI=4-(2,2'-联吡啶-3-乙炔基)-N-(吡啶-2-亚甲基)-N-(噻吩-3-亚甲基)苯胺,L2=4-(2,2'-联吡-3-乙炔基)-N-二(吡啶-2-亚甲基)-苯胺)都具有优良的电致发光(ECL)性能.在玻碳电极上,以TPrA为共反应物,其ECL电压分别在1.52和1.36 V左右,其最强的ECL发射波长在620~640 nm,且发光强度(I(ECL))与其浓度分别在0.2~1.6 μmol/L和0.02~2 μmol/L范围内呈良好的的线性关系.在相同条件下,配合物[Ir(yyp)2 L2](PF6)/TPrA体系的ECL强度比[Ir(ppy)2 L1](PF6)强,与[Ru(bpy)3](2+)/TPrA体系相当.

  17. 稠杂环化合物在红色磷光铱配合物中的应用%Application of Fused-Heterocyclic Compounds in Red Phosphorescent Iridium(Ⅲ) Complexes

    Institute of Scientific and Technical Information of China (English)

    王玲霞; 梅群波; 颜芳; 田波; 翁洁娜; 张彬; 黄维


    Organic light-emitting diodes (OLEDs) have attracted considerable attention during the last decade because of the potential advantages associated with their usage in full-color displays. Electroluminescent phosphorescent materials have also enjoyed similar levels of attention because of their excellent luminescent properties. The three primary colors, blue, green, and red, are essential for the practical application of phosphorescent complexes in flat-panel displays. Relative to the efficient green phosphorescent materials, red phosphorescent materials suffer many problems, including poor color purity, low efficiency, and low luminance, and the design of appropriate red colored materials therefore represents a significant challenge. Fused-heterocyclic compounds have been widely used in red phosphorescent iridium(Ⅲ) complexes because of their high quantum efficiency, color adjustability, and balanced charge injection and migration. This review summarizes the development and application of fused-heterocyclic compounds in recent years in small molecule, dendrimer and polymeric red phosphorescent iridium(Ⅲ) complexes. The influence of the molecular structures of iridium(Ⅲ) complexes on the optical and electrical properties and device performances has also been described. Finally, a discussion of the prospect of developing fused-heterocyclic compounds in the red phosphorescent materials has also been provided.%在过去的几十年里,有机发光二极管(OLED)由于潜在的优势,在全彩显示领域引起了高度重视.电致磷光材料因其优异的发光性能,引起了人们广泛关注.对于实际应用的平板显示器,蓝、绿、红三基色是必不可少的.相对于高效的绿光材料,红光磷光材料仍然存在色纯度差、效率低和亮度不足等问题,因此设计合适的红光材料成为具有挑战性的问题.稠杂环化合物因发光量子效率高、发光颜色可调、平衡电荷注入及迁移等优越性能而广泛

  18. Asymmetric Hydrogenation of Acetophenone and Its Derivatives Catalyzed by L-Proline Stabilized Iridium%L-脯氨酸稳定的铱催化苯乙酮及其衍生物不对称加氢反应

    Institute of Scientific and Technical Information of China (English)

    杨朝芬; 杨俊; 朱艳琴; 孙晓东; 李贤均; 陈华


    A supported iridium catalyst stabilized by L-proline was prepared under mild conditions and was applied to the heterogeneous asymmetric hydrogenation of acetophenone and its derivatives. The effect of the support and L-proline on the supported iridium catalyst was studied. The catalyst was characterized by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results showed that L-proline had a marked ability to stabilize and disperse the iridium particles. Reaction conditions for the asymmetric hydrogenation of acetophenone were examined in detail. LiOH enhanced the activity and enantioselectivity of the reaction. The alkali metal cation plays an important role in influencing the enantioselectivity. In addition, a synergistic effect between (1S,2S)-1,2-diphenyl-1,2-ethylenediamine ((1S,2S)-DPEN) and L-proline was observed, which significantly accelerated the reaction rate and enhanced the enantioselectivity. In the presence of (1S,2S)-DPEN as chiral modifier the catalyst 5% (w, mass fraction)lr/15(the molar ratio of L-proline to Ir) (L-Proline)-y-AI2C>3 exhibited good catalytic performance in the asymmetric hydrogenation of acetophenone and its derivatives. Under optimum conditions the enantiomeric excess (ee) values of (R)-phenylethanol and (f?)-2'-(trifluoromethyl) phenylethanol were 71.3% and 79.8%, respectively. Without using phosphine as a stabilizer the preparationof the catalyst was simple and the catalyst was reused several times without a significant loss In activity and enantioselectivity.%以L-脯氨酸为稳定剂制备了负载型金属铱催化剂,并用于苯乙酮及其衍生物不对称加氢反应.考察了载体以及L-脯氨酸的量对催化剂性能的影响,以透射电镜(TEM)和X射线光电子能谱(XPS)对催化剂进行了表征.结果表明L-脯氨酸对金属铱粒子具有较好的分散和稳定作用.通过考察反应条件发现:碱金属离子对反应有较大影响; L-脯氨酸与手性修饰

  19. Theoretical study on electronic structures and optical properties of blue phosphorescent Iridium(III) complexes with C{sup ∧}N and N{sup ∧}N ligands

    Energy Technology Data Exchange (ETDEWEB)

    Shang, Xiaohong [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); College of Chemistry and Life Science, Changchun University of Technology, Changchun 130024 (China); Liu, Yuqi; Qu, Xiaochun [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Wu, Zhijian, E-mail: [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)


    We report a quantum-chemical study on the electronic structures and optical properties of two series of heteroleptic iridium(III) complexes [(dfb-pz){sub 2}Ir(N{sup ∧}N+sub)], [dfb-pz=2,4-difluorobenzyl-N-pyrazole, sub indicates substituent group, N{sup ∧}N+sub=tphppz=4-tert-butyl-2-(5-phenyl-[1,2,4]triazol-3-yl)-pyridine (1a), tmppz=4-tert-butyl-2-(5-methyl-[1,2,4]triazol-3-yl)-pyridine (1b), fphppz=4-fluoro-phenyl-5-(2-pyridyl)pyrazole (1c), and fmphppz=4-trifluoromehtyl-phenyl-5-(2-pyridyl)pyrazole (1d)]; with [(C{sup ∧}N+sub){sub 2}Ir(fppz)], [C{sup ∧}N=b-pz=benzyl-N-pyrazole, fppz=3-trifluoromethyl-5-(2-pyridyl)pyrazole, C{sup ∧}N+sub=dfb-pz=2,4-difluorobenzyl-N-pyrazole (2a), tfmfb-pz=2-trifluoromethyl-5-fluorobenzyl-N-pyrazole (2b), phb-pz=3-phenyl-benzyl-N-pyrazole (2c), and dfphb-pz=3-phenyl-2,4-difluorobenzyl-N-pyrazole (2d)]. The calculated results shed light on the reasons of the remarkably manipulated excited-state and electroluminescent properties through substitution effect. The phenyl ring on main ligands can enhance the π-conjugation of the main ligands moiety and increase the metal-ligand bond strength for 2c and 2d, then enhancing the transition strength. From 1c, 1d, 2c, and 2d, it can also be seen that substituents on the terminal phenyl ring have a slight effect on the excited energy because the distance between the substituents and the ancillary (or main) ligand is interrupted by the phenyl moiety. The calculated absorption and luminescence properties of the four complexes 1a, 1b, 2a, and 2b are compared with the available experimental data and a good agreement is obtained. Furthermore, the assumed complex 1c, 2c, and 2d possess better charge transfer abilities and more balanced charge transfer rates. The designed complexes 2c and 2d are potential candidates for blue phosphorescent materials. -- Highlights: • Two series of electroluminescent iridium(III) complexes have been studied. • The charge transfer properties are affected

  20. Polymer light-emitting diodes based on cationic iridium(III) complexes with a 1,10-phenanthroline derivative containing a bipolar carbazole-oxadiazole unit as the auxiliary ligand (United States)

    Tang, Huaijun; Wei, Liying; Meng, Guoyun; Li, Yanhu; Wang, Guanze; Yang, Furui; Wu, Hongbin; Yang, Wei; Cao, Yong


    A 1,10-phenanthroline derivative (co-phen) containing a bipolar carbazole-oxadiazole unit was synthesized and used as the auxiliary ligand in cationic iridium(III) complexes [(ppy)2Ir(co-phen)]PF6 (ppy: 2-phenylpyridine) and [(npy)2Ir(co-phen)]PF6 (npy: 2-(naphthalen-1-yl)pyridine). Two complexes have high thermal stability with the glass-transition temperatures (Tg) of 207 °C and 241 °C, and the same 5% weight-reduction temperatures (ΔT5%) of 402 °C. Both of them were used as phosphorescent dopants in solution-processed polymer light-emitting diodes (PLEDs): ITO/PEDOT: PSS/PVK: PBD: complex (mass ratios 100: 40: x, x = 1.0, 2.0, and 4.0)/CsF/Al. The maximum luminances of the PLEDs using [(ppy)2Ir(co-phen)]PF6 and [(npy)2Ir(co-phen)]PF6 were 12567 cd m-2 and 11032 cd m-2, the maximum luminance efficiencies were 17.3 cd A-1 and 20.4 cd A-1, the maximum power efficiencies were 9.8 lm W-1 and 10.3 lm W-1, and the maximum external quantum efficiencies were 9.3% and 11.4% respectively. The CIE color coordinates were around (0.37, 0.57) and (0.44, 0.54) respectively, corresponding to the yellow green region.

  1. Crystal structure of (2,2′-bipyrid­yl)[2,6-bis­(1-butyl-1H-benzimidazol-2-yl)pyridine]­chlorido­iridium(III) tri­fluoro­methane­sulfonate (United States)

    Smith, Victoria I.; Zeller, Matthias


    The title complex compound, [Ir(C27H29N5)Cl(C10H8N2)](CF3SO3)2, was synthesized for a study of iridium(III)/periodate redox systems in water. The coordination geometry of the complex can be best described as distorted octa­hedral, with an r.m.s. deviation of 8.8 (8)% from ideal octa­hedral rectangular geometry. In the crystal, C—H⋯O and C—H⋯F inter­actions between the complex cation and the tri­fluoro­methane­sulfonate anions are observed, as well as a C—H⋯Cl inter­molecular inter­action between neighboring complex cations. In addition, the benzimidazole ring systems display parallel-displaced π–π stacking with centroid–centroid distances of 3.585 (3)–3.907 (3) Å. One of the two tri­fluoro­methane­sulfonate anions is disordered over two orientations with an occupancy ratio of 0.582 (6):0.418 (6). The title complex was characterized using FT–IR, cyclic voltammetry/rotating disc electrode polarography, fluorescence spectrometry, high resolution mass spectrometry, CHN elemental analysis and 1H NMR spectroscopy. PMID:28217326

  2. Electrocatalytic studies of iridium based clusters for the oxygen reduction and hydrogen oxidation reactions in 0.5 M H2SO4, in the presence of fuel cell contaminants

    Energy Technology Data Exchange (ETDEWEB)

    Uribe-Godinez, J.; Jimenez-Sandoval, O.; Borja-Arco, E.; Altamirano-Gutierrez, A. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Queretaro (Mexico); Castellanos, R.H. [Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada-Queretaro, Queretaro (Mexico)


    The development of a cost effective cathode catalyst which is tolerant to CH3OH is a priority for the development of proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). Ruthenium (Ru) and osmium nanoclusters are among the most promising alternatives to platinum (Pt) for the oxygen reduction reaction (ORR). However, iridium (Ir) is one of the most stable Pt group metals in acid media. Although it has a lower activity towards the ORR and hydrogen oxidation reaction (HOR) than platinum, its activity towards CH3OH is also lower than that of Pt. The synthetic procedure in this study was based on the pyrolysis of Ir4(CO)12 at 190 degrees C, under neutral (N2) and reductive atmospheres (H2) for 5 hours. The new materials were structurally characterized by FT-IR and micro-Raman spectroscopy, X-ray diffraction and scanning electron microscopy, and electrochemistry by the rotating disk electrode (RDE) technique in a 0.5 M H2SO4 electrolyte, at room temperature. This paper reported on the the electrokinetic parameters, such as the Tafel slope, the interchange current density and the transfer coefficient. It was concluded that the new materials are good candidates for their use as both anodes and cathodes as commercial platinum catalysts in PEMFC. All the new electrocatalysts performed the HOR, even in the presence of carbon monoxide, which is a clear advantage over Pt catalysts. 4 refs., 3 figs.

  3. Recovery from Iridium-192 flakes of a radioactive source for industrial use after a radiation incident; Recuperacion de hojuelas de Iridio-192 provenientes de una fuente radiactivas de uso industrial despues de un incidente radiologico

    Energy Technology Data Exchange (ETDEWEB)

    Cruz, W.H.; Zapata, L.A., E-mail:, E-mail: [Instituto Peruano de Energia Nuclear (GRRA/IPEN), Lima (Peru). Division de Gestion de Residuos Radiactivos


    The Iridium-192 ({sup 192}Ir) is the most used and ideal for industrial radiography applications, especially in petrochemical plants and pipelines and provides better contrast sensitivity for thick (25.4 mm). This source has constructive sealed double encapsulation, the internal capsule containing stainless steel to radioactive material in the form of flakes and welded with TIG process. The radiological incident happened at a gas station fuel sales in circumstances in which there was a homogeneity test welds a tank, the flakes or Ir-192 fell off his ponytail and left scattered over an area of 2 m{sup 2}, some fell flat areas and other land so collected in lead shielding and metal container and ground source. Full recovery of the leaflets was performed at the Division of radioactive waste management (GRRA) gaining a total of 22 flakes with no radiation risk to staff performance and installation and the conclusion was reached that the misapplicaion of TIG welding was the main cause the incident. (author)

  4. Study of electrocatalytic properties of iridium carbonyl cluster and rhodium carbonyl cluster compounds for the oxygen reduction and hydrogen oxidation reactions in 0.5 MH{sub 2}SO{sub 4} in presence and absence of methanol and carbon monoxide, respectively

    Energy Technology Data Exchange (ETDEWEB)

    Uribe-Godinez, J.; Borja-Arco, E.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)


    The suitability of carbonyl cluster compounds as a substitute to platinum (Pt) in fuel cell catalysts was investigated. Iridium (Ir{sub 4}(CO){sub 12} and rhodium (Rh{sub 6}(CO){sub 116}) cluster compounds were investigated as potential new electrocatalysts for oxygen reduction reaction (ORR) in the presence and absence of methanol at different concentrations, as well as for the hydrogen oxidation reaction (HOR) with pure hydrogen and a hydrogen/carbon monoxide mixture. The materials were studied using room temperature rotating disk electrode (RDE) measurements and cyclic and linear sweep voltammetry techniques (LSV). Tafel slope and exchange current density were calculated using the LSV polarization curves. Cyclic voltamperometry results suggested that the electrocatalysts were tolerant to methanol. However, electrochemical behaviour of the materials altered in the presence of CO, and peaks corresponding to CO oxidation were observed in both cases. The rhodium carbonyl showed a higher current density for the ORR than the iridium carbonyl. The current potential curves in the presence of methanol were similar to those obtained without methanol. Results confirmed the tolerance properties of the materials to perform the ORR. Decreased current density values were observed during HOR, and were attributed to changes in the hydrogen solubility and diffusion coefficient due to the presence of CO. The Tafel slopes indicated that the mechanics of the HOR were Heyrovsky-Volmer. Results showed that the materials are capable of performing both ORR and HOR in an acid medium. It was noted that the iridium carbonyl cluster followed a 4-electron transfer mechanism towards the formation of water. It was concluded that the compounds are suitable for use as both cathodes and anodes in proton exchange membrane fuel cells (PEMFCs) and as cathodes in direct methanol fuel cells (DMFCs). 3 refs., 2 tabs., 3 figs.

  5. Highly Phosphorescent Iridium Complex for Organic Light Emitting Diodes%高效磷光铱配合物的合成及电致发光性能研究

    Institute of Scientific and Technical Information of China (English)

    李春香; 胡嘉伟; 孙培培; 潘毅; 郑建鸿


    合成了一种含苯并噻唑结构配体的环金属化铱配合物(ffbi)2Ir(acac),(其中ffbi为1-(4-氟苄基)-2-(4-氟苯基)苯并咪唑,acac 为乙酰丙酮),并以其作为发光体,制备了有机电致发光器件.结果表明该配合物具有强磷光发光特性,器件发绿色光.其中结构为TCTA(40nm)/CBP:Ir(6.3%,30nm)/BCP(10nm)/Alq(40nm)的电致发光器件在12V电压下最大发光亮度达41499 cd·m-2,在8V电压下,最大外量子效率达5.7%.%A bis-cyclometalated iridium complex(ffbi)2Ir(acac)(ffbi=l-(4-fluorobenzyl)-2-(4-fluorophenyl)benzimidazole,acac=acetylacetone)containing benzimidazole-based ligand has been synthesized and used as an emitter in organic light emitting diodes(OLEDs).The results showed that this complex had a strong phosphorescent character and the EL devices based on this complex emitted green light.For the device with the structure of TCTA(40nm)/CBP:Ir(6.3%,30nm)/BCP(10nm)/Alq(40nm),the maximum brightness reached 41499 cd·m-2 at a voltage of 12 V and the maximum external efficiency reached 5.7%at a voltage of 8 V.

  6. Synthesis and characterization of carbazolide-based iridium PNP pincer complexes. Mechanistic and computational investigation of alkene hydrogenation: evidence for an Ir(III)/Ir(V)/Ir(III) catalytic cycle. (United States)

    Cheng, Chen; Kim, Bong Gon; Guironnet, Damien; Brookhart, Maurice; Guan, Changjian; Wang, David Y; Krogh-Jespersen, Karsten; Goldman, Alan S


    New carbazolide-based iridium pincer complexes ((carb)PNP)Ir(C2H4), 3a, and ((carb)PNP)Ir(H)2, 3b, have been prepared and characterized. The dihydride, 3b, reacts with ethylene to yield the cis-dihydride ethylene complex cis-((carb)PNP)Ir(C2H4)(H)2. Under ethylene this complex reacts slowly at 70 °C to yield ethane and the ethylene complex, 3a. Kinetic analysis establishes that the reaction rate is dependent on ethylene concentration and labeling studies show reversible migratory insertion to form an ethyl hydride complex prior to formation of 3a. Exposure of cis-((carb)PNP)Ir(C2H4)(H)2 to hydrogen results in very rapid formation of ethane and dihydride, 3b. DFT analysis suggests that ethane elimination from the ethyl hydride complex is assisted by ethylene through formation of ((carb)PNP)Ir(H)(Et)(C2H4) and by H2 through formation of ((carb)PNP)Ir(H)(Et)(H2). Elimination of ethane from Ir(III) complex ((carb)PNP)Ir(H)(Et)(H2) is calculated to proceed through an Ir(V) complex ((carb)PNP)Ir(H)3(Et) which reductively eliminates ethane with a very low barrier to return to the Ir(III) dihydride, 3b. Under catalytic hydrogenation conditions (C2H4/H2), cis-((carb)PNP)Ir(C2H4)(H)2 is the catalyst resting state, and the catalysis proceeds via an Ir(III)/Ir(V)/Ir(III) cycle. This is in sharp contrast to isoelectronic (PCP)Ir systems in which hydrogenation proceeds through an Ir(III)/Ir(I)/Ir(III) cycle. The basis for this remarkable difference is discussed.

  7. Selectivity in C-alkylation of dianions of protected 6-methyluridine

    Directory of Open Access Journals (Sweden)

    Ngoc Hoa Nguyen


    Full Text Available A regioselective synthesis of 6-ω-alkenyluridines 3, precursors of potent antiviral and antitumor cyclonucleosides 5, is described. While ω-alkenyl halides do not alkylate 6-lithiouridine, compounds 3 were prepared in a regioselective manner by sequential treatment of 6-methyluridine 2 with LTMP or LDA (4 equiv in THF at −30 °C followed by alkylation with ω-alkenyl bromides.

  8. Structural elucidation and physicochemical properties of mononuclear Uranyl(VI) complexes incorporating dianionic units (United States)

    Azam, Mohammad; Velmurugan, Gunasekaran; Wabaidur, Saikh Mohammad; Trzesowska-Kruszynska, Agata; Kruszynski, Rafal; Al-Resayes, Saud I.; Al-Othman, Zeid A.; Venuvanalingam, Ponnambalam


    Two derivatives of organouranyl mononuclear complexes [UO2(L)THF] (1) and [UO2(L)Alc] (2), where L = (2,2′-(1E,1′E)-(2,2-dimethylpropane-1,3-dyl)bis(azanylylidene, THF = Tetrahydrofuran, Alc = Alcohol), have been prepared. These complexes have been determined by elemental analyses, single crystal X-ray crystallography and various spectroscopic studies. Moreover, the structure of these complexes have also been studied by DFT and time dependent DFT measurements showing that both the complexes have distorted pentagonal bipyramidal environment around uranyl ion. TD-DFT results indicate that the complex 1 displays an intense band at 458.7 nm which is mainly associated to the uranyl centered LMCT, where complex 2 shows a band at 461.8 nm that have significant LMCT character. The bonding has been further analyzed by EDA and NBO. The photocatalytic activity of complexes 1 and 2 for the degradation of rhodamine-B (RhB) and methylene blue (MB) under the irradiation of 500W Xe lamp has been explored, and found more efficient in presence of complex 1 than complex 2 for both dyes. In addition, dye adsorption and photoluminescence properties have also been discussed for both complexes. PMID:27595801

  9. Ru alkylidene compounds bearing tridentate, dianionic ligands: Lewis acid activation and olefin metathesis. (United States)

    McKinty, Adam M; Stephan, Douglas W


    The series of tridentate complexes of Ru-alkylidenes (L)Ru(CHPh)(SCH2CH2)2E (E = O, L = SIMes 1, PCy3 2, E = S, L = SIMes 3, PCy3 4; E = PPh 7, L = PCy3), (L)Ru(CHPh)(SC6H4)2S (L = SIMes 5, PCy3 6), (L)Ru(CHPh) (OCH2CH2)2O (L = SIMes 8, PCy3 9) were prepared and shown to react with one equivalent of BCl3 to give the complexes (L)Ru(CHPh)Cl[E(CH2CH2S)2BCl2] (E = O, L = SIMes 10, PCy3 11, E = S, L = SIMes 12a/b, PCy3 13, E = PPh, L = PCy3 16) and (L)Ru(CHPh)(SC6H4)2O (L = SIMes 14, PCy3 15). In the case of 1 and 2 reaction with two equivalents of BCl3 affording the corresponding cation via chloride abstraction. These cations coordinate MeCN to give the six coordinate Ru cation salts [(L)Ru(CHPh)- (NCMe)(O(CH2CH2S)2BCl2)][BCl4] L = SIMes 17, PCy3 18). The generated five coordinate cations derived from 2-9 via addition of two equivalents of BCl3 were evaluated in standard preliminary tests for olefin metathesis catalysis.

  10. Structural elucidation and physicochemical properties of mononuclear Uranyl(VI) complexes incorporating dianionic units (United States)

    Azam, Mohammad; Velmurugan, Gunasekaran; Wabaidur, Saikh Mohammad; Trzesowska-Kruszynska, Agata; Kruszynski, Rafal; Al-Resayes, Saud I.; Al-Othman, Zeid A.; Venuvanalingam, Ponnambalam


    Two derivatives of organouranyl mononuclear complexes [UO2(L)THF] (1) and [UO2(L)Alc] (2), where L = (2,2‧-(1E,1‧E)-(2,2-dimethylpropane-1,3-dyl)bis(azanylylidene, THF = Tetrahydrofuran, Alc = Alcohol), have been prepared. These complexes have been determined by elemental analyses, single crystal X-ray crystallography and various spectroscopic studies. Moreover, the structure of these complexes have also been studied by DFT and time dependent DFT measurements showing that both the complexes have distorted pentagonal bipyramidal environment around uranyl ion. TD-DFT results indicate that the complex 1 displays an intense band at 458.7 nm which is mainly associated to the uranyl centered LMCT, where complex 2 shows a band at 461.8 nm that have significant LMCT character. The bonding has been further analyzed by EDA and NBO. The photocatalytic activity of complexes 1 and 2 for the degradation of rhodamine-B (RhB) and methylene blue (MB) under the irradiation of 500W Xe lamp has been explored, and found more efficient in presence of complex 1 than complex 2 for both dyes. In addition, dye adsorption and photoluminescence properties have also been discussed for both complexes.

  11. Structure and reactivity of a pyridine-1-imido-2-thiolato complex of iridium(III), CpIr(1-N-2-Spy), generated by photolysis of the (azido)(pyridine-2-thiolato) complex, CpIr(2-Spy)(N3). (United States)

    Sekioka, Yusuke; Kaizaki, Sumio; Mayer, James M; Suzuki, Takayoshi


    Photolysis of the (azido)(pyridine-2-thiolato)iridium(III) complex CpIr(2-Spy)(N3) (1) gave a pyridine-1-imido-2-thiolato complex, CpIr(1-N-2-Spy) (2), in which one of the nitrogen atoms of the azide ligand has been inserted into the Ir-N(py) bond (Cp = eta5-C5Me5). Complex 2 reacted quantitatively with methyl iodide to give the N-methylated product, [CpIr(1-NMe-2-Spy)]I (3). X-ray crystallography revealed that both 2 and 3 have similar two-legged piano stool structures with planar 1-N-2-Spy2- or 1-NMe-2-Spy- ligands, which form iridacyclopentadienyl-like rings by moderate S(ppi)/N(ppi) to Ir(dpi) pi donation.

  12. Study on floatation separation of iridium in potassium iodide-tetrabutyl ammonium bromide-water system%碘化钾-四丁基溴化铵-水体系浮选分离铱的研究

    Institute of Scientific and Technical Information of China (English)

    李玉玲; 司学芝; 梁晨曦; 马万山


    The separation behaviors and conditions of iridium from other metal ions were studied in potassium iodide-tetrabutyl ammonium bromide-water system. The results showed that Ir(Ⅳ) could form water insoluble ternary complex ([Irl6 ][TBAB]2) with tetrabutyl ammonium bromide and potassium iodide in aqueous solution. This ternary complex floated on water phase, and the liquid-solid twophase was formed with clear interface. When the concentrations of tetrabutyl ammonium bromide and potassium iodide were 8. 0 × 10-4 mol/L and 6. 0 × 10-3 mol/L, the flotation rate of Ir(Ⅳ) was up to 97. 6 %. Meanwhile, Rh(Ⅲ), W(Ⅳ) V(Ⅴ), Ce(Ⅲ), Sn(Ⅳ), Mo(Ⅵ), U(Ⅵ), Ga(Ⅲ), Cr(Ⅲ), Mn(Ⅱ), Al(Ⅲ), Fe(Ⅱ),Zn(Ⅱ) , Co(Ⅱ) and Ni(Ⅱ) were not floated in this system, realizing the quantitative separation of Ir(Ⅳ) from these metal ions. Bi(Ⅲ), Sb(Ⅲ) and Hg(Ⅱ) had high flotation rate in this system. Pb(Ⅱ) and Cu(Ⅱ) could react with KI to form water insoluble PbI2 and CuI, so Ir(Ⅳ) could not be separated from Pb(Ⅱ), Cu(Ⅱ),Bi(Ⅲ) , Sb(Ⅲ) and Hg(Ⅱ). The synthetic water sample was separated by this method with satisfactory results.%研究了碘化钾-四丁基溴化铵-水体系分离Ir(Ⅳ)的行为及Ir(Ⅳ)与其他金属离子分离的条件.实验结果表明,在水溶液中,Ir(Ⅳ)与四丁基溴化铵(TBAB)和碘化钾形成不溶于水的三元缔合物[IrI6][TBAB]2,此三元缔合物浮于水相上层形成界面清晰的液-固两相.当溶液中四丁基溴化铵和碘化钾的浓度分别为8.0×10-4mol/L和6.0×10-2 mol/L,Ir(Ⅳ)的浮选率达到97.6%,而Rh(Ⅲ)、W(Ⅵ)、V(Ⅴ)、Ce(Ⅲ)、Sn(Ⅳ)、Mo(Ⅵ)、U(Ⅵ)、Ga(Ⅲ)、Cr(Ⅲ)、Mn(Ⅲ、Al(Ⅲ)、Fe(Ⅱ)、Zn(Ⅱ)、Co(Ⅱ)和Ni(Ⅱ)离子在该体系中不被浮选,实现了Ir(Ⅳ)与这些金属离子的定量分离.Bi(Ⅲ)、Sb(Ⅲ)和Hg(Ⅱ)在该体系中有很高的浮选率,Pb(Ⅱ)和Cu(Ⅱ)与KI反应生成不溶于水的PbI2和CuI,所以Ir(Ⅳ)不能和Pb(Ⅱ),Cu(

  13. Synthesis and Luminescence Property of Two New Blue Phosphorescent Iridium( Ⅲ ) Diazine Complexes%新型蓝色磷光嘧啶铱(Ⅲ)配合物的合成及发光性质

    Institute of Scientific and Technical Information of China (English)

    葛国平; 李春艳; 郭海清


    We designed and synthesized two new indium ( IH ) diazine complexes [ (DFPPM)2IrCl-(PPh3)] and [ (DFPPM)2Ir(CN) (PPh3) ], where Ph = pheny], containing2-(2,4-difluorophenyl)-pyrimidine (DFPPM) as the cyclometalated ligands. OLEDs with iridium( III ) diazine complexes as phosphor have high-efficiency and long luminance half-life, however, diazine compounds show a significantly redshift of the emission band than pyridine compounds. Therefore, it will be a great challenge to synthesize blue phosphorescent materials with diazine compounds as ligands. The complexes were characterized by nuclear magnetic resonance ( NMR) spectroscopy and mass spectrometry (MS) and their photophysical properties were investigated by UV-Vis spectroscopy and photolumi-nescence (PL) technique. The PL spectrum of [ (DFPPM ),IrCl(PPh3) ] in solution has its maximum emission peak at 472 nm and 489 nm, whereas [ ( DFPPM) 2Ir( CN) (PPh3) ] has its maximum emission peak at 447 nm and 472 nm. The luminescence of [ (DFPPM) 2IrCl( PPh3) ] shifts lothe blue region compared to that of (DFPPM)2Ir(acac) , indicating that the HOMO-LUMO gap is increased due to the higher ligand field strength of the phosphine. Compared with [ ( DFPPM )2IrCl-(PPh3) ] , [ ( DFPPM)2 Ir( CN) ( PPh3) ] shows a significantly blue-shift of the emission band. The ligand field strength of CN is larger than Cl due to its strong a donor and -rr acceptor ability. This causes larger splitting of the d-orbital and consequently more lowering of the metal-centered HOMO. Complex of ( DFPPM)2lr( CN) ( PPh3) emits deep blue light with Commission Internationale de l'Eclairage (CIE) coordinates of (0. 14, 0. 15). Electroluminescence (EL) device was fabricated when the complex of [ ( DFPPM) 2Ir( CN) (PPh3) ] was doped into polymer host polyvinylcarbazole (PVK). Compared to the photoluminescence spectrum, a red-shifted of emission was observed from the electroluminescence spectrum. The reason of red-shift of EL spectra is in progress

  14. GFAAS Determination of Platinum, Palladium, Rhodium and Iridium in Ores%石墨炉原子吸收光谱法测定矿石中铂、钯、铑、铱

    Institute of Scientific and Technical Information of China (English)

    羊波; 杨新周; 李银科; 叶艳清; 胡秋芬


    矿石样品铂、钯、铑和铱经铅试金富集,所得金属合粒用硝酸-盐酸溶解,用石墨炉原子吸收光谱法测定矿石样品中铂、钯、铑和铱的含量。在优化的石墨炉工作条件下测得:铂的质量浓度在20-150μg·L-1、钯在15-120μg·L-1、铑和铱在6-100μg·L-1范围内与其吸光度呈线性关系,检出限(3s/k)依次为4.6,4.0,1.5,1.5μg·L-1。方法用于分析了2种矿石国家标准物质(GBW07341、GBW07342),测定结果与认定值相符。方法的回收率在87.6%~105.5%之间。测定值的日内和日间相对标准偏差(n=7)分别在2.8%~3.6%和3.5%~4.7%之间。%Platinum, palladium, rhodium and iridium in ore samples were enriched by the lead fire assaying method, and the alloy of precious metals obtained was dissolved in HNO3 and HCl. The contents of Pt, Pd, Rh and Ir in the sample solution were determined by GFAAS. It was found that under the optimum working conditions of the graphite furnace, linear relationships between values of absorbance and mass concentration were obtained in the ranges of 20--150 μg·L-1 for Pt, 15--120μg·L-1 for Pd, 6-100 μg·L-1 for Rh and It. Detection limits (3s/ k) found were 4. 6/lg ~ L-1 (Pt), 4. 0μg·L-1(Pd) and 1.5μg·L-1(Rh and It). The proposed method was used in the analysis of 2 ore CRM's (GBW 07341, GBW 07342) and the results obtained were in conformity with the certified values. Values of recovery found by standard addition method were in the range of 87. 6%--105. 5%. Values of intra-day and inter-day RSD's (n=7) found were in the ranges of 2. 8%--3. 6% and 3. 5%--4. 7% respectively.

  15. Semiconductor films on flexible iridium substrates (United States)

    Goyal, Amit


    A laminate semiconductor article includes a flexible substrate, an optional biaxially textured oxide buffer system on the flexible substrate, a biaxially textured Ir-based buffer layer on the substrate or the buffer system, and an epitaxial layer of a semiconductor. Ir can serve as a substrate with an epitaxial layer of a semiconductor thereon.

  16. Iridium catalysed synthesis of piperazines from diols

    DEFF Research Database (Denmark)

    Nordstrøm, Lars Ulrik Rubæk; Madsen, Robert


    A green and atom-economical method has been developed for the synthesis of piperazines by cyclocondensation of diols and amines in aqueous media in the presence of a catalytic amount of [Cp*IrCl2]2....

  17. Hexanuclear Iridium Clusters Supported on Magnesium Oxide

    NARCIS (Netherlands)

    Koningsberger, D.C.; Maloney, S.D.; Kelley, M.J.; Gates, B.C.


    [Ir4(C0)12o] n the surface of MgO reacts to give [HIr4(CO)ll]-,w hich upon treatment with co at 200 OC gives [Ir6(C0)15]2- on the surface in high yield. Treatment of the latter with a solution of [PPN][CI] leads to extraction of [Ir6(C0)15]2b-y cation metathesis. The surface-bound [Ir6(CO)15]2w- as

  18. Hexanuclear Iridium Clusters Supported on Magnesium Oxide

    NARCIS (Netherlands)

    Koningsberger, D.C.; Maloney, S.D.; Kelley, M.J.; Gates, B.C.


    [Ir4(C0)12o] n the surface of MgO reacts to give [HIr4(CO)ll]-,w hich upon treatment with co at 200 OC gives [Ir6(C0)15]2- on the surface in high yield. Treatment of the latter with a solution of [PPN][CI] leads to extraction of [Ir6(C0)15]2b-y cation metathesis. The surface-bound [Ir6(CO)15]2w- as

  19. Saved by Iridium? An Alternative to GPS (United States)


    Groups of GPS Vulnerabilities Hostile Attacks Controllable Risks Other Vulnerabilities Direct or Kinetic Environmental Effects Self-Induced Directed...Constellation GONASS GALILEO BEIDOU-2 IRNSS GROUND BASED RADIO NAVIGATION LORAN LACATA VHF DME INS AUTOMATIC NAVIGATION TERCOM DESMAC PTAN Radio...0 0 1 0 1 LACATA 0 0 1 1 0 2 VHF 0 1 1 1 0 3 DME 0 1 1 1 0 3 INS 0 0 1 1 1 3 AUTOMATIC NAVIGATION TERCOM 0 0 1 1 1 3 DESMAC 0 0 1 1 1 3 PTAN 0

  20. Organometallic half-sandwich iridium anticancer complexes

    NARCIS (Netherlands)

    Liu, Z.; Habtemariam, A.; Pizarro, A.M.; Fletcher, S.A.; Kisova, A.; Vrana, O.; Salassa, L.; Bruijnincx, P.C.A.|info:eu-repo/dai/nl/33799529X; Clarkson, G.J.; Brabec, V.; Sadler, Peter J.


    The low-spin 5d6 IrIII organometallic half-sandwich complexes [(η5-Cpx)Ir(XY)Cl]0/+, Cpx = Cp*, tetramethyl(phenyl)cyclopentadienyl (Cpxph), or tetramethyl(biphenyl)cyclopentadienyl (Cpxbiph), XY = 1,10-phenanthroline (4−6), 2,2′-bipyridine (7−9), ethylenediamine (10 and 11), or picolinate (12−14),

  1. Luminescent iridium complexes for detection of molybdate. (United States)

    Castillo, Carmen E; Davies, David L; Klair, Anne-K Duhme; Singh, Kuldip; Singh, Shalini


    Reactions of [Ir(C^N)(2)Cl](2) [HC^N = 2-(3-R-phenyl)pyridine, 2-(3-R-phenylpyrazole) R = H, Me] with Me(2)-phencat give luminescent complexes [Ir(C^N)(2)(Me(2)-phencat)][PF(6)] (Me(2)-2a, b, c)[PF(6)]. Deprotection of the methoxy groups with BBr(3) is problematic as simultaneous bromination of the cyclometallated phenyl groups occurs. However, deprotection of Me(2)-phencat with BBr(3) followed by complexation with [Ir(C^N)(2)Cl](2) gives luminescent complexes [Ir(C^N)(2)(H(2)-phencat)][PF(6)] (H(2)-3a, c)[PF(6)], which are luminescent sensors for molybdate.

  2. Recrystallization of deformed single crystals of iridium

    Energy Technology Data Exchange (ETDEWEB)

    Ermakov, A.V.; Klotsman, S.M.; Pushin, V.G.; Timofeev, A.N.; Kaigorodov, V.N.; Panfilov, P.Y.; Yurchenko, L.I.


    The X-ray diffractometric method was used to analyze crystalline textures that appear during rolling of pure single-Ir and annealing of the said crystals in ultrahigh vacuum (UHV) at successively elevating temperatures. Observing alteration of the texture of the deformed pure single-Ir after UHV annealing, the primary recrystallization temperature T{sub 1recr} of pure Ir was found not to exceed 670 K (0.25 T{sub m}).

  3. Thermophysical properties of iridium at finite temperature (United States)

    Kumar, Priyank; Bhatt, N. K.; Vyas, P. R.; Gohel, V. B.


    The bulk properties of materials in an extreme environment such as high temperature and high pressure can be understood by studying anharmonic effects due to the vibration of lattice ions and thermally excited electrons. In this spirit, in the present paper, anharmonic effects are studied by using the recently proposed mean-field potential (MFP) approach and Mermin functional which arise due to the vibration of lattice ions and thermally excited electrons, respectively. The MFP experienced by a wanderer atom in the presence of surrounding atoms is constructed in terms of cold energy using the local form of the pseudopotential. We have calculated the temperature variation of several thermophysical properties in an extreme environment up to melting temperature. The results of our calculations are in excellent agreement with the experimental findings as well as the theoretical results obtained by using first principle methods. We conclude that presently used conjunction scheme (MFP+pseudopotential) is simple computationally, transparent physically, and accurate in the sense that the results generated are comparable and sometimes better than the results obtained by first principle methods. Local pseudopotential used is transferable to extreme environment without adjusting its parameters. Project supported by the Department of Science and Technology-Fund for Improvement of Science and Technology Infrastructure Project (DST-FIST) (Level 1) of Department of Sciences and Technology (DST), New Delhi (Grant No. SR/FST/PST-001/2006).

  4. Determination of Ruthenium, Rhodium, Palladium, Iridium and Platinum in Copper-Nickel Sulfide Ores by Bismuth-Antimony Fire Assay%铋锑试金测定硫化铜镍矿中钌铑钯铱铂

    Institute of Scientific and Technical Information of China (English)

    李可及; 刘淑君; 邵坤


    建立了用于预富集硫化铜镍矿中钌铑钯铱铂5种铂族元素的铋锑试金方法。40.0 g 氧化铋、25.0 g硼酸、10.0 g 碳酸钠、1.00 g 淀粉与10.0 g 待测样品于120 mL 瓷皿中,充分混匀,850℃入炉,20 min 后升至1000℃,保留40 min,出炉后趁热倾倒熔渣,使铋试金于空气中自然冷却。设计两段灰吹流程,铋试金先在镁砂灰皿内灰吹,直至剩余直径约5 mm,而后直接转入盛有20 g 熔融锑粉的坩埚盖中继续灰吹,获得直径约1 mm 的试金合粒。所得合粒经微波消解,冷却后定容至10 mL。铂钯用 ICP-OES 分析;钌铑铱质量数选择99 Ru,103 Rh 和191 Ir,以115 In 和185 Re 为内标,应用 ICP-MS 分析。对标准物质 GBW07196平行测定12次,铂族元素相对标准偏差为7.0%~9.5%。在10 g 取样量条件下,方法对 Ru, Rh, Pd, Ir 和 Pt 的检出限分别为0.027,0.016,0.11,0.10和0.11 ng/ g。应用本方法处理标准物质 GBW07194,GBW07195和 GBW07196均获得了满意的结果。%A bismuth-antimony fire assay method for the preconcentration of ruthenium, rhodium, palladium, iridium and platinum in copper-nickel sulfide ores was developed. 40. 0 g bismuth trioxide, 25. 0 g boric acid, 10. 0 g sodium carbonate and 1. 00 g starch were mixed with 10. 0 g sample in a 120 mL porcelain bowl, which was put in a furnace at 850 ℃. After 20 min the temperature was raised to 1000 ℃ and held for another 40 min, and then the bowl was taken out, with the slag poured, which left the bismuth button to air cooling. A two-step cupellation procedure was developed. During the first step, the bismuth button was cupellated in a magnesia cupel until its diameter reached 5 mm or so, then it was transferred to a crucible cover containing 20 g melting antimony and kept cupellating, at last a bead with a diameter of 1 mm was obtained. The bead was microwave-digested, after cooling down to room temperature, the solvent of which was transferred to a volumetric flask and

  5. Iridium/Iridium Silicide as an Oxidation Resistant Capping Layer for Soft X-ray Mirrors

    Energy Technology Data Exchange (ETDEWEB)

    Prisbrey, S; Vernon, S


    Rust on a sword, tarnish on the silverware, and a loss in reflectivity for soft x-ray mirrors are all caused by oxidation that changes the desired characteristics of a material. Methods to prevent the oxidation have varied over the centuries with the default method of a protective coating being the most common. The protective coating for x-ray mirrors is usually a self-limiting oxidized layer on the surface of the material that stops further oxidation of the material by limiting the diffusion of oxygen to the material underneath.

  6. 一种红光树枝状铱配合物的合成、表征及其对Hg2+的识别研究%A Dendritic Red Iridium Complex: Synthesis, Characterization and Hg2+ Recognition Properties

    Institute of Scientific and Technical Information of China (English)

    李襄宏; 赵鑫帝; 吕康乐; 张爱清


    本文基丁二Ir(Btp)2(acac)为发光内核,合成了一种外围为萘环的苄醚型树枝状红光铱配合物,并通过NMR、MS和元素分析实验表征了该配合物.利用紫外-可见吸收光谱与磷光光谱实验研究了该配合物对金属离子的识别作用.结果表明:在CH3CN/THF溶液中,仪Hg2+的加入能引起配合物的最大吸收峰和发射峰均发生蓝移,溶液颜色由桔黄色变为浅绿色.该配合物可作为识别汞离子的光化学传感器.%A Ir(Btp)2(acac) cored red dendrimer with benzyloxy-based dendrons bearing naphthyl peripheral group was synthesized and characterized by NMR, MS and element analysis experiments. The metal ions recognition properties were investigated by absorption and emission spectra. Only upon addition of Hg2+, obvious blue-shifts both in absorption spectra and emission spectra were observed with the color of the CH3CN/THF solution changing from orange-yellow to light green. The results demonstrated that an optical chemo-sensor for Hg2+ based on the iridium(Ⅲ) dendrimer was realized.

  7. Multimetallic ruthenium(II) complexes based on biimidazole and bibenzimidazole: Effect of dianionic bridging ligands on Redox and spectral properties

    Energy Technology Data Exchange (ETDEWEB)

    Rillema, D.P.; Sahai, R.; Matthews, P.; Edwards, A.K.; Shaver, R.J.; Morgan, L. (Univ. of North Carolina, Charlotte (USA))


    The preparation and properties of ruthenium(II) complexes containing the ligands 2,2{prime}-biimidazole (BiImH{sub 2}), 2,2{prime}-bibenzimidazole (BiBzImH{sub 2}), and 2,2{prime}-bipyridine (bpy) are reported. The complexes described are ((Ru(bpy){sub 2}){sub 2}BiIm){sup 2+} and the series (Ru-(bpy){sub n}(BiImH{sub 2}){sub 3{minus}n}){sup 2+}, (Ru(bpy){sub n}(BiBzImH{sub 2}){sub 3{minus}n}){sup 2+}, and (Ru(bpy){sub n}(BiBzImRu(bpy){sub 2}){sub 3{minus}n}){sup 2+}, n = 0-2. The redox potential for the first Ru{sup 3+/2+} couple shifted negatively from 1.26 to {minus}0.26 V vs SSCE as bpy ligands were replaced by BiImH{sub 2}, BiBzImH{sub 2}, and BiBzImRu(bpy){sub 2} ligands. Reductions were found in the {minus}1.5- to {minus}1.6-V range for complexes containing bypyridine ligands, but none were observed out to {minus}2.0 V for (Ru(BiImH{sub 2}){sub 3}){sup 2+} or (Ru(BiBzImH{sub 2}){sub 3}){sup 2+}. The complexes absorbed energy in the visible and UV regions of the spectrum and emitted radiation, with the exception of the tetrametallic species, in the 600-800-nm region. Estimates of the excited-state redox potentials revealed that the excited-state species were powerful reductants, but were weak oxidants. The (Ru{sup III}-(BiBzImRu{sup II}(bpy){sub 2}){sub 3}){sup 3+} cation absorbed in the near-infrared region at 12.2 {times} 10{sup 3} cm{sup {minus}1} in acetonitrile, but the absorption disappeared upon reduction to (Ru{sup II}(BiBzImRu{sup II}(bpy){sub 2}){sub 3}){sup 2+}. The position of the absorption manifold maximum varied linearly with the static and optical dielectric constant of the solvent. 45 refs., 12 figs., 3 tabs.

  8. Synthesis and Optoelectronic Properties of a Red-Emitting Iridium(III) Complex Containing 1-Phenylpyrazole%以1-苯基吡唑为主配体的红光Ir(III)配合物的合成及光电特性

    Institute of Scientific and Technical Information of China (English)

    任静琨; 许慧侠; 屈丽桃; 郝玉英; 王华; 许并社


      合成了一种新型红色磷光配合物二(1-苯基咪唑)(1-苯基异喹啉)合铱((ppz)2Ir(piq)),通过核磁共振氢谱(1H NMR)对其结构进行了表征,通过紫外-可见(UV-Vis)吸收光谱、荧光光谱、低温磷光光谱、循环伏安法及含时密度泛函理论(TD-DFT)对其光物理性能及能级结构进行了研究.制备了一系列基于(ppz)2Ir(piq)的电致发光器件,研究了(ppz)2Ir(piq)的电致发光性质.结果表明,(ppz)2Ir(piq)的UV-Vis吸收峰主要位于296、342、395和460 nm,固态粉末的室温磷光发射峰位于618 nm,在2-甲基四氢呋喃(2-MeTHF)溶液中其低温磷光发射峰位于598 nm,其三线态能级(ET)为2.07 eV.(ppz)2Ir(piq)的最高占据轨道(HOMO),其主要定域于配体ppz和金属Ir(III)上,最低未占据轨道(LUMO)主要定域于配体piq上.(ppz)2Ir(piq)的HOMO和LUMO能级分别为-5.92和-3.62 eV.基于(ppz)2Ir(piq)电致发光器件的优化掺杂浓度为8%-12%(w),最大电致发光谱峰位于616 nm,最大电流效率约10 cd·A-1,最大功率效率为4.44 lm·W-1,色坐标保持在(0.65,0.35)附近,是一种潜在的饱和红光磷光材料.%The synthesis, characterization, photophysical and electrophosphorescent properties of iridium(III) complex [(ppz)2Ir(piq)] (ppz=1-phenylpyrazole, piq=1-phenylisoquinoline) are reported. The structure was defined by proton nuclear magnetic resonance (1H NMR). The photophysical properties and energy-level structure of [(ppz)2Ir(piq)] are studied by ultraviolet-visble (UV-Vis) absorption, fluorescence, and phosphorescent spectroscopies at 77 K, cyclic voltammetry (CV), and time-dependent density functional theory (TD-DFT) calculation. The electroluminescent properties of [(ppz)2Ir(piq)] using 4,4ʹ-bis(9-carbazolyl)-1, 1ʹ-biphenyl (CBP) as a host are investigated. Absorption bands of [(ppz)2Ir(piq)] are located at about 296, 342, 395, and 442 nm. [(ppz)2Ir(piq)] exhibits red phosphorescent emission with a peak at 618 nm in CH2Cl2 solution

  9. Study on the electronic structures of Iridium-doped SmOFeAs under the strongly correlated electrons effects%强关联效应下非磁性元素Ir掺杂的SmFeAsO电子结构理论研究

    Institute of Scientific and Technical Information of China (English)

    潘敏; 黄整; 赵勇


    基于密度泛函理论,采用广义梯度近似方法(SGGA+U )计算分析了SmOFeAs电子结构以及Ir掺杂对该体系晶体结构和电子结构的影响。结果表明,随着Ir的掺杂, SmOFeAs晶体结构中FeAs层与SmO层之间的耦合增强,晶体内部所含的铁砷四面体随着Ir掺杂其畸变性程度逐步减小。 Fe3d以及As4p杂化轨道对体系电子结构起主要影响作用。 Ir掺杂所引入的电子使FeAs层的巡游电子增多、Fe3d轨道中的 d z2轨道离域性增强。当Ir掺杂量为20%时,费米面处于电子态密度峰值附近,费米面急剧变化使该体系的Tc值有所增高,反映了体系费米能级移动与其超导电性的密切关联性。计算的电子态密度与XPS所得价带谱实验结果一致,进一步验证了采用SGGA+U方法其包含修正d轨道局域电子的库仑势,使得计算结果与实验结果更加接近。%Based on the consideration of strong correlation of electrons, we have used density functional theory generalized gradient ap-proximation method SGGA+U to calculate SmFeAsO and Ir doping effects on the lattices and electronic properties. It is found that iridium doping at the Fe site enhances the interaction between FeAs and SmO layers and results in a modification of the FeAs4 tetrahedron. The electronic density of states (DOS) of SmOFe1−x Irx As is studied by comparing the calculations with the X-ray photoe-mission spectroscopy experiments (XPS). It is revealed that the Fe 3d and As 4p hybridization orbits dominate the electric properties for SmOFe1−x Irx As. Ir doping makes the five orbitals of Fe3d all filled. Superconductivity is sensitive to the peak position shifting away from Fermi level. Our VASP SGGA+U calculation provides a better agreement with the experimental results when we use an on-site coulomb energy of U on Fe 3d shell, which is sharply contrasted to the GGA process.

  10. Platinum and Iridium Coatings Obtained by Double Glow Plasma Technology

    Institute of Scientific and Technical Information of China (English)

    WU Wangping; CHEN Zhaofeng; CHEN Zhou; CONG Xiangna; QIU Jinlian


    Pt and Ir coatings were produced by double glow plasma technology on the surface of Ti alloy substrates.The chemical compositions of the coatings were determined by X-ray diffraction and X-ray photoelectron spectroscopy.The microstructure and morphology of the coatings were observed by scanning electron microscopy.The hardness and elastic modulus of the coatings were estimated by nanoindentation.The measurements of adhesive forces of the coatings were performed with scratch tester.The results indicated that the Pt and Ir coatings displayed the preferred (220) orientation due to the initial nuclei with preferred growth on the surface of the substrates.The interface between the Pt coating and substrate exhibited no evidence of delamination.The Ir coating was composed of irregular columnar grains with many nanovoids at the interface between the coating and substrate.The mean values of hardness for Pt and Ir coatings were 0.9 GPa and 9 GPa,respectively.The elastic modulus of Pt and Ir coatings were 178 GPa and 339 GPa,respectively.The adhesive forces of the Pt and Ir coatings were about 66.4 N and 55 N,respectively.The Pt and Ir coatings adhered well to the Ti alloy substrates.

  11. Deformation change in light iridium nuclei from laser spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Verney, D.; Le Blanc, F.; Obert, J.; Oms, J.; Puteaux, J.C.; Roussiere, B.; Sauvage, J. [IN2P3-CNRS/Universite Paris Sud-XI, Institut de Physique Nucleaire, Orsay Cedex (France); Cabaret, L.; Duong, H.T.; Pinard, J. [CNRS, Laboratoire Aime Cotton, Orsay Cedex (France); Crawford, J.E.; Lee, J.K.P. [McGill University, Physics Department, Montreal (Canada); Fricke, B.; Rashid, K. [Institut fuer Theoretische Physik der Universitaet Kassel, Kassel (Germany); Genevey, J.; Ibrahim, F. [IN2P3-CNRS/Universite Joseph Fourier-Grenoble I, Laboratoire de Physique Subatomique et de Cosmologie, Grenoble Cedex (France); Huber, G.; Krieg, M.; Sebastian, V. [Institut fuer Physik der Universitaet Mainz, Mainz (Germany); Le Scornet, G.; Lunney, D. [IN2P3-CNRS/Universite Paris Sud-XI, Centre de Spectrometrie Nucleaire et de Spectrometrie de Masse, Orsay Cedex (France)


    Laser spectroscopy measurements have been performed on neutron-deficient and stable Ir isotopes using the COMPLIS experimental setup installed at ISOLDE-CERN. The radioactive Ir atoms were obtained from successive decays of a mass-separated Hg beam deposited onto a carbon substrate after deceleration to 1kV and subsequently laser desorbed. A three-color, two-step resonant scheme was used to selectively ionize the desorbed Ir atoms. The hyperfine structure (HFS) and isotope shift (IS) of the first transition of the ionization path 5d{sup 7}6s{sup 24}F{sub 9/2}{yields}5d{sup 7}6s6p{sup 6}F{sub 11/2} at 351.5nm were measured for {sup 182-189}Ir, {sup 186}Ir{sup m} and the stable {sup 191,193}Ir. The nuclear magnetic moments {mu}{sub I} and the spectroscopic quadrupole moments Q{sub s} were obtained from the HFS spectra and the change of the mean square charge radii from the IS measurements. The sign of {mu}{sub I} was experimentally determined for the first time for the masses 182{<=}A{<=}189 and the isomeric state {sup 186}Ir{sup m}. The spectroscopic quadrupole moments of {sup 182}Ir and {sup 183}Ir were measured also for the first time. A large mean square charge radius change between {sup 187}Ir and {sup 186}Ir{sup g} and between {sup 186}Ir{sup m} and {sup 186}Ir{sup g} was observed corresponding to a sudden increase in deformation: from {beta}{sub 2}{approx_equal}+0.16 for the heavier group A = 193, 191, 189, 187 and 186m to {beta}{sub 2}{>=}+0.2 for the lighter group A=186g, 185, 184, 183 and 182. These results were analyzed in the framework of a microscopic treatment of an axial rotor plus one or two quasiparticle(s). This sudden deformation change is associated with a change in the proton state that describes the odd-nuclei ground state or that participates in the coupling with the neutron in the odd-odd nuclei. This state is identified with the {pi}3/2 {sup +}[402 ] orbital for the heavier group and with the {pi}1/2{sup -}[541 ] orbital stemming from the 1h{sub 9/2} spherical subshell for the lighter group. That last state seems to affect strongly the observed values of the nuclear moments. (orig.)

  12. Reactive oxygen species in iridium-based OER catalysts


    Pfeifer, Verena; Jones, Travis E.; Wrabetz, Sabine; Massué, Cyriac; Velasco Vélez, Juan J.; Arrigo, Rosa; Scherzer, Michael; Piccinin, Simone; Hävecker, Michael; Knop-Gericke, Axel; Schlögl, Robert


    Tremendous effort has been devoted towards elucidating the fundamental reasons for the higher activity of hydrated amorphous IrIII/IV oxyhydroxides (IrOx) in the oxygen evolution reaction (OER) in comparison with their crystalline counterpart, rutile-type IrO2, by focusing on the metal oxidation state. Here we demonstrate that, through an analogy to photosystem II, the nature of this reactive species is not solely a property of the metal but is intimately tied to the electronic structure of o...

  13. C-NH2 bond formation mediated by iridium complexes


    Mena, Inmaculada; Casado, Miguel A.; Polo, Víctor; García-Orduña, P.; Lahoz, Fernando J.; Oro, Luis A.


    In the presence of phosphanes (PR3), the amido-bridged trinuclear complex [{Ir(μ-NH2)(tfbb)}3] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2-η2-4-κ-C12H8F 4N)(PR3)3], which are the products of the C-N coupling between the amido moiety and a vinylic carbon of the diolefin. An alternative synthetic approach to these species involves the reaction of the 18-e- complex [Ir(Cl)(tfbb)(PMePh2)2] with gaseous ammonia and additional phosphane. DFT studies show ...

  14. C-NH2 bond formation mediated by iridium complexes. (United States)

    Mena, Inmaculada; Casado, Miguel A; Polo, Víctor; García-Orduña, Pilar; Lahoz, Fernando J; Oro, Luis A


    In the presence of phosphanes (PR3 ), the amido-bridged trinuclear complex [{Ir(μ-NH2 )(tfbb)}3 ] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2-η(2) -4-κ-C12 H8 F4 N)(PR3 )3 ], which are the products of the CN coupling between the amido moiety and a vinylic carbon of the diolefin. An alternative synthetic approach to these species involves the reaction of the 18 e(-) complex [Ir(Cl)(tfbb)(PMePh2 )2 ] with gaseous ammonia and additional phosphane. DFT studies show that both transformations occur through nucleophilic attack. In the first case the amido moiety attacks a diolefin coordinated to a neighboring molecule following a bimolecular mechanism induced by the highly basic NH2 moiety; the second pathway involves a direct nucleophilic attack of ammonia to a coordinated tfbb molecule. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Reactive oxygen species in iridium-based OER catalysts. (United States)

    Pfeifer, Verena; Jones, Travis E; Wrabetz, Sabine; Massué, Cyriac; Velasco Vélez, Juan J; Arrigo, Rosa; Scherzer, Michael; Piccinin, Simone; Hävecker, Michael; Knop-Gericke, Axel; Schlögl, Robert


    Tremendous effort has been devoted towards elucidating the fundamental reasons for the higher activity of hydrated amorphous Ir(III/IV) oxyhydroxides (IrO x ) in the oxygen evolution reaction (OER) in comparison with their crystalline counterpart, rutile-type IrO2, by focusing on the metal oxidation state. Here we demonstrate that, through an analogy to photosystem II, the nature of this reactive species is not solely a property of the metal but is intimately tied to the electronic structure of oxygen. We use a combination of synchrotron-based X-ray photoemission and absorption spectroscopies, ab initio calculations, and microcalorimetry to show that holes in the O 2p states in amorphous IrO x give rise to a weakly bound oxygen that is extremely susceptible to nucleophilic attack, reacting stoichiometrically with CO already at room temperature. As such, we expect this species to play the critical role of the electrophilic oxygen involved in O-O bond formation in the electrocatalytic OER on IrO x . We propose that the dynamic nature of the Ir framework in amorphous IrO x imparts the flexibility in Ir oxidation state required for the formation of this active electrophilic oxygen.

  16. The Marine Geochemistry of Rhenium, Iridium and Platinum (United States)


    in the boundary clay, and proposed that this was the result of the impact of a 10 km meteorite with the Earth (Alvarez et al. 1980). Subsequently, Ir...Esser, B. K. (1991). Osmium Isotope Geochemistry of Terrigenous and Marine Sediments. PhD thesis, Yale University. Felitsyn, S. B. and P. A. Vaganov...C. E. (1990). Rhenium- Osmium Isotope Geochemistry of the Mantle, PhD Thesis, Yale University. McCallum, M. E., R. R. Loucks, R. R. Carlson, E. F

  17. Microwave hyperthermia radiosensitized iridium-192 for recurrent brain malignancy. (United States)

    Borok, T L; Winter, A; Laing, J; Paglione, R; Sterzer, F; Sinclair, I; Plafker, J


    Twenty-one patients whose solitary detectable biopsy proven recurrent brain malignancies produced Central Nervous System (CNS) symptoms warranting further intervention received 60-minute 43 degrees C (180 degree-minute) interstitial 2450 MHz microwave hyperthermia fractions. All received brain teletherapy prior to recurrence. The first 15 received no brachytherapy and served as a toxicity pilot. All 15 enjoyed neurologic improvement, 12 symptomatic improvement, and 12 objective response as mass reduction and/or tumor necrosis. The next 6 patients were selected with more favorable Karnofsky performance status, no known active malignancy elsewhere, and received afterloading Ir-192 interstitial implantation juxtaposed to radiosensitizing hyperthermia. Volume dose varied from 1000 to 2245 rad, and dose rate from 40 to 100 rad/hr. Dose selected varied as a function of pre-recurrence teletherapy dose, general condition, histologic type, and volume. Neurosurgical debulking, if technically indicated through no additional aperture or trauma, was permitted if consistent with preservation of neurological function. Six enjoyed neurologic improvement, symptom reduction, and objective tumor response; three remain alive, and one experienced transient improvement. Complications, histologic subtypes, autopsy findings, stereotactic approach, thermal monitoring methods and CT follow-up of objective response are presented along with computer dosimetry and isotherm chart. Our microtraumatic universal catheter technique for CT guided stereotactic biopsy, aspiration, decompression, thermal sensory loop, thermalization antennae, and brachytherapy without multiple trauma nor changing catheters is stressed. The rationale for combined modes peculiar to the CNS will be outlined.2+ Proposal for incorporating controlled-release ARA-C chemotherapy polymer micro-rods into the interstitial format will be offered. The preceeding is an FDA-approved controlled clinical trial.(ABSTRACT TRUNCATED AT 250 WORDS)

  18. Electrochemical water oxidation with carbon-grafted iridium complexes. (United States)

    deKrafft, Kathryn E; Wang, Cheng; Xie, Zhigang; Su, Xin; Hinds, Bruce J; Lin, Wenbin


    Hydrogen production from water splitting provides a potential solution to storing harvested solar energy in chemical fuels, but this process requires active and robust catalysts that can oxidize water to provide a source of electrons for proton reduction. Here we report the direct, covalent grafting of molecular Ir complexes onto carbon electrodes, with up to a monolayer coverage. Carbon-grafted Ir complexes electrochemically oxidize water with a turnover frequency of up to 3.3 s(-1) and a turnover number of 644 during the first hour. Electrochemical water oxidation with grafted catalysts gave enhanced rates and stability compared to chemically driven water oxidation with the corresponding molecular catalysts. This strategy provides a way to systematically evaluate catalysts under tunable conditions, potentially providing new insights into electrochemical water oxidation processes and water oxidation catalyst design.

  19. Radiation Parameters of High Dose Rate Iridium -192 Sources (United States)

    Podgorsak, Matthew B.

    A lack of physical data for high dose rate (HDR) Ir-192 sources has necessitated the use of basic radiation parameters measured with low dose rate (LDR) Ir-192 seeds and ribbons in HDR dosimetry calculations. A rigorous examination of the radiation parameters of several HDR Ir-192 sources has shown that this extension of physical data from LDR to HDR Ir-192 may be inaccurate. Uncertainty in any of the basic radiation parameters used in dosimetry calculations compromises the accuracy of the calculated dose distribution and the subsequent dose delivery. Dose errors of up to 0.3%, 6%, and 2% can result from the use of currently accepted values for the half-life, exposure rate constant, and dose buildup effect, respectively. Since an accuracy of 5% in the delivered dose is essential to prevent severe complications or tumor regrowth, the use of basic physical constants with uncertainties approaching 6% is unacceptable. A systematic evaluation of the pertinent radiation parameters contributes to a reduction in the overall uncertainty in HDR Ir-192 dose delivery. Moreover, the results of the studies described in this thesis contribute significantly to the establishment of standardized numerical values to be used in HDR Ir-192 dosimetry calculations.

  20. Photocatalytic transformations catalyzed by inorganic semiconductors and iridium complexes


    Cherevatskaya, Maria


    Chapter 1 provides an overview on the organic synthesis mediated by heterogeneous photocatalysts reviewing recent advances and discussing the underlying photocatalytic mechanisms. Heterogeneous photocatalysis is applicable for a wide range of organic transformations from oxidations and reductions to carbon-heteroatom and carbon-carbon bond forming reactions including enantioselective examples. The wide variety of accessible heterogeneous semiconductor photocatalysts with different redox poten...

  1. High Surface Iridium Anodes for Molten Oxide Electrolysis Project (United States)

    National Aeronautics and Space Administration — Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith...

  2. Dosimetry of IRIDIUM-192 and CESIUM-137 Seed Sources. (United States)

    Thomason, Cynthia

    The use of ^{192}Ir in brachytherapy implants both alone and in conjunction with other modalities for the treatment of various types of cancer has greatly increased in recent years. This increased usage has led to a greater need for detailed information concerning the dose distribution surrounding commerically available ^{192} Ir seed sources. This is especially truce since improvements in computer technology along with their increased availability and utilization have enabled more precise calculation of dose distributions. The radiation does distribution in water was measured using LiF thermoluminescent dosimeters for an ^{192}Ir seed source with platinum encapsulation, for an ^{192}Ir seed source with stainless steel encapsulation and for a ^{137}Cs seed source intended as a substitute for ^{192 }Ir. The Electron-Gamma-Shower (EGS) computer code, which is a package for doing Monte Carlo simulation of the transport of photons and electrons in any medium or geometry specified by the user, also was used to study the dose distribution around these seed sources. In addition, the exposure rate constant, exposure rate at 1 meter, transmission through the source capsule, f-factor, and energy distribution exiting the source capsule were evaluated by Monte Carlo simulation of these three sources. Good agreement was seen between the measured data and the Monte Carlo generated data. In addition to producing valuable dosimetric data, this study has demonstrated that Monte Carlo modeling of ^{192} Ir and ^{137}Cs seed sources using the EGS Monte Carlo code can provide an accurate means of evaluating these data.

  3. Electronic and Magnetic Properties of Small Iridium Clusters

    Institute of Scientific and Technical Information of China (English)

    KUANG Xiang-jun


    The electronic and magnetic properties of small IrN clusters (N=5, 6, 9, 13, and 19 ) are studied by using the discrete-variational local-spin-density-functional method. The equilibrium bond length in the chosen geometry for IrN clusters are determined and show bond contraction compared with the bulk interatomic spacing. The clusters with magnetic ground state have ferromagnetic interaction and their average magnetic moment per atom has a complex size dependence. At last, the reactivity of IrN clusters toward H2, N2 and CO molecules is predicted.

  4. Which alternative methods to the iridium gamma-graphy?; Quelles methodes alternatives a la gammagraphie a l'iridium?

    Energy Technology Data Exchange (ETDEWEB)

    Hatsch, J.; Chauveau, D.; Blettner, A. [Institut de Soudure, 93 - Villepinte (France)


    Gamma-graphy is a very widely used process for testing welded steel constructions, pipings, pressure vessels, frameworks and particularly welds in them. The major disadvantage of this NDT method lies in the risks due to ionizing radiations requiring the setting up of a safety perimeter being a constraint to the owner or involving a shift system for the personnel and thus heavy indirect expenditures. In addition, the recent French regulatory pressure as for transport, storage, and radioactive sources management make their use still more complicated under industrial conditions and their setting up more and more expensive. It seems difficult that only one NDT technique could a substitute for gamma-graphy. Various alternative solutions are possible. Their setting up depends on the type of component to be inspected, on the nature of material, on the type of welding (butt weld, nozzle), on the orientation and position of the defects to be detected as well as their environment. This conference surveys the techniques liable to substitute for gamma-graphy as well as their scope of application and the hindrances limiting their development. (authors)

  5. 基于面式-三(2-(4-三氟甲基苯基)吡啶)合铱配合物为发光中心的高效绿光有机电致发光器件%Efficient Green Organic Light-Emitting Diodes with fac-Tris(2-(4-trifluoromethylphenyi)pyridine)iridium Complex as Emitter

    Institute of Scientific and Technical Information of China (English)

    滕明瑜; 王铖铖; 荆一铭; 郑佑轩; 林晨


    用经典的方法合成了面式-三(2-(4-三氟甲基苯基)吡啶)合铱配合物(fac-Ir(tfmppy)3),并得到了其晶体结构.在CH2Cl2溶液中Ir(tfmppy)3的发射光谱显示出了峰值位于525 nm的π→π*跃迁吸收以及金属到配体电荷转移(MLCT)吸收,色坐标(CIE)为(o.31,0.62),量子效率计算为4.59%(以Ru(bpyh]Cl2为参照).以Ir(ffmppy)3为发光中心,制备并研究了有机电致发光器件:ITO/rAPC (60 nm)/Ir(tfmppy)3 (x%):mCP (30 nm)/TPBi (60 nm)/LiF(1 nm)/Al (100 nm).4%掺杂浓度的器件在.4 197 cd·m-2的亮度下显示的最大电流效率为33.95 cd·A-1,在12.7 V时的最大亮度为43 612 cd·m-2,色坐标(CIE)为(0.31,0.61).利用瞬态电致发光法(transient electroluminescence (TEL))、在1 300 (V·cm-1)1/2的电场强度下 Ir(tfmppy)3配合物的电子迁移率测定为4.24× 10-6 cm2·(V·s)-1.非常接近于常用的电子传输材料八羟基喹啉铝(Alq3的电子迁移率.%fac-Tris(2-(4-trifluoromethylphenyl)pyridine)iridium (Ir(tfmppy)3) was prepared by conventional method and its crystal structure was determined.Excitation at either r→πr* or MLCT absorption band of Ir (tfmppy)3 in CH2Cl2 solution leads to the same MLCT emission maxima at 525 nm with Commission Interuationale de L'Eclairage (CIE) coordinates of (0.31,0.62) and the emission quantum yield is 4.59% in CH2C12 (by reference to an aerated aqueous solution of [Ru (bpy)3]Cl2 as the standard solution).Organic light-emitting diodes (OLEDs) based on the green electrophosphorescent complex in ITO/TAPC (1,1-bis [4-[N,N-di(p-tolyl)amino]phenyl]cyclohexane,60 nm)/Ir (tfmppy)3 (x%):mCP (1,3-bis (carbazol-9-yl)benzene,30 nm)/TPBi (2,2',2"-(1,3,5-benzinetriyl)-tris (1-phenyl-1-H-benzimidazole,60 nm)/LiF (1 nm)/Al (100 nm) were investigated.The device with 4% dopant concentration shows a maximum current efficiency of 33.95 cd·A-1 at 4 197 cd· m-2,a maximum brightness of 43 612 cd·m-2 at 12.7 V,and CIE coordinates of (0.31,0.61).The device

  6. Probing the lowest coordination number of dianionic platinum-cyanide complexes in the gas phase: Dynamics of the charge dissociation process

    DEFF Research Database (Denmark)

    Bojesen, G; Hvelplund, P; Jørgensen, Thomas J. D.


    in Pt(CN)(5)(2-) and Pt(CN)(4)(2-), but no indication of the existence of Pt(CN)(3)(2-) was found. This indicates that the lifetime of Pt(CN)(3)(2-) is less than 4 mus (the flight time from the collision region to the detector). In contrast, all monoanion platinum-cyanide complexes were observed, i...

  7. Photoelectron spectroscopy and ab initio study of the doubly antiaromatic B(6) (2-) dianion in the LiB(6) (-) cluster. (United States)

    Alexandrova, Anastassia N; Boldyrev, Alexander I; Zhai, Hua-Jin; Wang, Lai-Sheng


    A metal-boron mixed cluster LiB(6) (-) was produced and characterized by photoelectron spectroscopy and ab initio calculations. A number of electronic transitions were observed and used to compare with theoretical calculations. An extensive search for the global minimum of LiB(6) (-) was carried out via an ab initio genetic algorithm technique. The pyramidal C(2v) ((1)A(1)) molecule was found to be the most stable at all levels of theory. The nearest low-lying isomer was found to be a triplet C(2) ((3)B) structure, 9.2 kcal/mol higher in energy. Comparison of calculated detachment transitions from LiB(6) (-) and the experimental photoelectron spectra confirmed the C(2v) pyramidal global minimum structure. Natural population calculation revealed that LiB(6) (-) is a charge-transfer complex, Li(+)B(6) (2-), in which Li(+) and B(6) (2-) interact in a primarily ionic manner. Analyses of the molecular orbitals and chemical bonding of B(6) (2-) showed that the planar cluster is twofold (pi- and sigma-) antiaromatic, which can be viewed as the fusion of two aromatic B(3) (-) units.

  8. Ligand-solvent interactions in a highly reduced metal chelate complex: medium dependence of the one-electron reduction of the bis(maleonitriledithiolato)gold dianion. (United States)

    LeSuer, Robert J; Geiger, William E


    The one-electron reduction of [Au(mnt)(2)](2-) (mnt = [S(2)C(2)(CN)(2)](2-), maleonitriledithiolate), 1(2-), stands out in the rich redox chemistry of metal-mnt complexes as a chemically reversible but electrochemically irreversible process. Although the E(1/2) value of the primary redox reaction 1(2-)/1(3-) is only slightly medium dependent (ca. -1.36 V to -1.53 V vs FcH in several nonaqueous solvents and supporting electrolytes), its chemical reversibility is dramatically solvent dependent. A quasi-Nernstian process was observed only in tetrahydrofuran (THF) at low supporting electrolyte concentrations. Fast reversible follow-up reactions, ascribed to formation of solvento-complexes [Au(mnt)(2).Solv](3-), were observed through cyclic voltammetry (CV) studies in dichloromethane and acetonitrile. The specifically solvated trianion reverts to "unsolvated" 1(2-) when reoxidized, accounting for the overall chemical reversibility of the process. Owing to the fact that the ligands in 1(3-) are highly negatively charged, the strong specific solvation is likely to involve H-bonding interactions between the solvent and the sulfur atoms of the trianion. Ion-pairing interactions between 1(3-) and electrolyte cations were also shown to have a discernible effect on the 1(2-)/1(3-) couple in THF. The heterogeneous electron-transfer (ET) rate constant (k(s)) for this couple was sufficiently low (k(s) = approximately 10(-3) cm s(-1)) to suggest a square-planar to quasi-tetrahedral structural rearrangement being intrinsic to the 1(2-)/1(3-) ET process. The E(1/2) separation between the 1(-)/1(2-) and 1(2-)/1(3-) couples (ca. 220 mV) is much smaller than any of those previously reported for metal-mnt complexes. The behavior of the gold-mnt trianion is a rare example of a ligand-based solvento-complex, which contrasts with the well-known metal-based solvento-complexes that are commonly observed between electron-deficient complexes and strong donor solvents.

  9. One-Dimensional Coordination Polymers of Lanthanide Cations to Cucurbit[7]uril Built Using a Range of Tetrachloride Transition-Metal Dianion Structure Inducers

    Directory of Open Access Journals (Sweden)

    Sai-Feng Xue


    Full Text Available A number of linear coordination polymers have been assembled from lanthanide cations (Ln3+ and cucurbit[7]uril (Q[7] in the presence of [CuCl4]2−or [CoCl4]2− anions acting as inorganic structure inducers in HCl solution. X-ray diffraction analysis has revealed that they form three groups of isomorphous structures. Generally, the complexes of Q[7] with light lanthanide cations (those with atomic number below that of neodymium (Nd3+ are in one group. The other two groups, in which the lanthanide cation has atomic number greater than that of europium (Eu3+, seem to follow no obvious rule. For example, the complexes of Q[7] with Eu3+ and Gd3+cations are in the second group in the presence of [CuCl4]2− anions, while they are in the third group in the presence of [CoCl4]2− anions. However, whatever group a given complex belongs to, they all show a common honeycomb-patterned supramolecular assembly, in which [CuCl4]2−or [CoCl4]2− anions form a honeycomb structure. The Ln3+ cations then coordinate to neighboring Q[7] molecules to form 1D coordination polymers that are inserted into the channels of the honeycomb framework, such that each individual coordination polymer is surrounded by [CuCl4]2−or [CoCl4]2− anions.

  10. A Highly Efficient Heterogenized Iridium Complex for the Catalytic Hydrogenation of Carbon Dioxide to Formate. (United States)

    Park, Kwangho; Gunasekar, Gunniya Hariyanandam; Prakash, Natarajan; Jung, Kwang-Deog; Yoon, Sungho


    A heterogenized catalyst on a highly porous covalent triazine framework was synthesized and characterized to have a coordination environment similar to that of its homogeneous counterpart. The catalyst efficiently converted CO2 into formate through hydrogenation with a turnover number of 5000 after 2 h and an initial turnover frequency of up to 5300 h(-1) ; both of these values are the highest reported to date for a heterogeneous catalyst, which makes it attractive toward industrial application. Furthermore, the synthesized catalyst was found to be stable in air and was recycled by simple filtration without significant loss of catalytic activity.

  11. Synthesis and Photophysical Properties of Novel Red Light-Emitting Cyclometalated Iridium(Ⅲ) Complexes

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Xiao-Wei; YANG,Chu-Luo; LI,Zhong-An; HUANG,Bing; QIN,Jin-Gui


    @@ Considerable research is currently focused on the organic electrophosphorescent materials due to their high luminescent efficiency. Electrophosphorescent material based on heavy metal complexes is a hot topic in the research of organic light-emitting devices (OLEDs). We synthesized a series of novel cyclometalated heavy metal complexes by introducing pheny-quinoline moieties into ligands by means of a convenient method (Scheme 1), and investigated their photophysical properties which indicated that those compounds exhibited red light-emitting and high luminescent efficiency.These complexes have been characterized by 1H NMR, UV-vis and PL.

  12. Patient-specific dose calculation methods for high-dose-rate iridium-192 brachytherapy (United States)

    Poon, Emily S.

    In high-dose-rate 192Ir brachytherapy, the radiation dose received by the patient is calculated according to the AAPM Task Group 43 (TG-43) formalism. This table-based dose superposition method uses dosimetry parameters derived with the radioactive 192Ir source centered in a water phantom. It neglects the dose perturbations caused by inhomogeneities, such as the patient anatomy, applicators, shielding, and radiographic contrast solution. In this work, we evaluated the dosimetric characteristics of a shielded rectal applicator with an endocavitary balloon injected with contrast solution. The dose distributions around this applicator were calculated by the GEANT4 Monte Carlo (MC) code and measured by ionization chamber and GAFCHROMIC EBT film. A patient-specific dose calculation study was then carried out for 40 rectal treatment plans. The PTRAN_CT MC code was used to calculate the dose based on computed tomography (CT) images. This study involved the development of BrachyGUI, an integrated treatment planning tool that can process DICOM-RT data and create PTRAN_CT input initialization files. BrachyGUI also comes with dose calculation and evaluation capabilities. We proposed a novel scatter correction method to account for the reduction in backscatter radiation near tissue-air interfaces. The first step requires calculating the doses contributed by primary and scattered photons separately, assuming a full scatter environment. The scatter dose in the patient is subsequently adjusted using a factor derived by MC calculations, which depends on the distances between the point of interest, the 192Ir source, and the body contour. The method was validated for multicatheter breast brachytherapy, in which the target and skin doses for 18 patient plans agreed with PTRAN_CT calculations better than 1%. Finally, we developed a CT-based analytical dose calculation method. It corrects for the photon attenuation and scatter based upon the radiological paths determined by ray tracing. The scatter dose is again adjusted using our scatter correction technique. The algorithm was tested using phantoms and actual patient plans for head-and-neck, esophagus, and MammoSite breast brachytherapy. Although the method fails to correct for the changes in lateral scatter introduced by inhomogeneities, it is a major improvement over TG-43 and is sufficiently fast for clinical use.

  13. A fourth-generation iridium-192 source-based CT scanner for brachytherapy (United States)

    Berndt, Anita Glenda

    This thesis describes and characterizes the sub-systems (source, detectors, data acquisition system and collimator) of a prototype fourth generation computed tomography scanner consisting of a ring of 96 8-channel photodiode scintillator (CdW04) detectors. The 192Ir brachytherapy source and transport mechanism of a commercial high-dose-rate treatment unit provides the photons for measuring projections of the scanned object. It is envisioned that the tomographic images generated with this scanner will be used to plan high-dose-rate brachytherapy treatments. Prototype detectors responded linearly to an incident gamma-ray fluence over a wide dynamic range (2.6 decades). The noise analysis of the prototype detectors indicated that the detector noise is dominated by quantum noise for incident gamma-ray intensities expected when imaging patients up to about 45 cm in diameter. A pair of lead rings collimates both the source and the detectors to provide a maximum scan field of view 50 cm in diameter. The full-widths at half-maximum of the radiation sensitivity and image (slice) sensitivity profiles in the longitudinal direction are 2.7 cm and 0.4 cm respectively. High contrast resolution, image noise and radiation dose were investigated using a combination of measurements and computer simulations. Computer simulations were performed to assess the effect of varying detector number, source size and number of source positions. The high contrast resolution was examined by modeling wire phantoms, and images of uniform Plexiglas disks were used to quantify the scanner noise. The fullwidth at half-maximum of the point spread function was found to be 0.21 cm using source and detector dimensions of 0.36 cm and 0.275 cm respectively (768 detectors, 864 source positions). This configuration resulted in a standard deviation of 23 Hounsfield units at the center of a 25 cm diameter Plexiglas phantom for a 7.5 Ci 192Ir source. The multiple-scan average dose for a 100 second scan (1.0 cm slice spacing, 2.7 cm slice thickness) measured using prototype collimators is 1.1 cGy. The high contrast resolution and image noise are adequate for visualizing brachytherapy implants and contrast filled critical organs for planning brachytherapy treatments. Preliminary images clearly show streak free visualization of objects containing high Z materials.

  14. Mechanistic investigation of the iridium-catalysed alkylation of amines with alcohols


    Fristrup, Peter; Tursky, Matyas; Madsen, Robert


    The [Cp*IrCl2]2-catalysed alkylation of amines with alcohols was investigated using a combination of experimental and theoretical methods. A Hammett study involving a series of para-substituted benzyl alcohols resulted in a line with a negative slope. This clearly documents that a positive charge is built up in the transition state, which in combination with the measurement of a significant kinetic isotope effect determines hydride abstraction as being the selectivity-determining step under t...

  15. Mild, reversible reaction of iridium(III) amido complexes with carbon dioxide. (United States)

    Dobereiner, Graham E; Wu, Jianguo; Manas, Michael G; Schley, Nathan D; Takase, Michael K; Crabtree, Robert H; Hazari, Nilay; Maseras, Feliu; Nova, Ainara


    Unlike some other Ir(III) hydrides, the aminopyridine complex [(2-NH(2)-C(5)NH(4))IrH(3)(PPh(3))(2)] (1-PPh(3)) does not insert CO(2) into the Ir-H bond. Instead 1-PPh(3) loses H(2) to form the cyclometalated species [(κ(2)-N,N-2-NH-C(5)NH(4))IrH(2)(PPh(3))(2)] (2-PPh(3)), which subsequently reacts with CO(2) to form the carbamato species [(κ(2)-O,N-2-OC(O)NH-C(5)NH(4))IrH(2)(PPh(3))(2)] (10-PPh(3)). To study the insertion of CO(2) into the Ir-N bond of the cyclometalated species, a family of compounds of the type [(κ(2)-N,N-2-NR-C(5)NH(4))IrH(2)(PR'(3))(2)] (R = H, R' = Ph (2-PPh(3)); R = H, R' = Cy (2-PCy(3)); R = Me, R' = Ph (4-PPh(3)); R = Ph, R' = Ph (5-PPh(3)); R = Ph, R' = Cy (5-PCy(3))) and the pyrimidine complex [(κ(2)-N,N-2-NH-C(4)N(2)H(3))IrH(2)(PPh(3))(2)] (6-PPh(3)) were prepared. The rate of CO(2) insertion is faster for the more nucleophilic amides. DFT studies suggest that the mechanism of insertion involves initial nucleophilic attack of the nitrogen lone pair of the amide on CO(2) to form an N-bound carbamato complex, followed by rearrangement to the O-bound species. CO(2) insertion into 1-PPh(3) is reversible in the presence of H(2) and treatment of 10-PPh(3) with H(2) regenerates 1-PPh(3), along with Ir(PPh(3))(2)H(5).

  16. Diene-ligated iridium catalyst for allylation reactions of ketones and imines. (United States)

    Barker, Timothy J; Jarvo, Elizabeth R


    [Ir(cod)Cl](2) is a highly reactive catalyst for allylation reactions of ketones using allylboronic ester. Mechanistic experiments are consistent with formation of a nucleophilic allyliridium(I) complex that is activated by the diene ligand toward attack of a ketone. Aryl and alkyl ketones react smoothly at room temperature. Aldimines also undergo allylation under these reaction conditions, requiring increased reaction times relative to the corresponding ketones.

  17. Relativistic configuration interaction calculation on the ground and excited states of iridium monoxide

    CERN Document Server

    Suo, Bingbing; Han, Huixian


    We present the fully relativistic multi-reference configuration interaction calculations of the ground and low-lying excited electronic states of IrO for individual spin-orbit component. The lowest states for four spin-orbit components 1/2, 3/2, 5/2, and 7/2 are calculated intensively to clarify the ground state of IrO. Our calculation suggests that the ground state is of 1/2 spin-orbit component, which is highly mixed with $^4\\Sigma^-$ and $^2\\Pi$ states in $\\Lambda-S$ notation. The two low-lying states of the 5/2 and 7/2 spin-orbit components are nearly degenerate with the ground state and locate only 234 and 260 cm$^{-1}$ above, respectively. The equilibrium bond length 1.712 \\AA \\ and harmonic vibrational frequency 903 cm$^{-1}$ of the 5/2 spin-orbit component are close to the experimental measurement of 1.724 \\AA \\ and 909 cm$^{-1}$, which suggests the 5/2 state should be the low-lying state contributed to spectra in experimental study. Moreover, the electronic states that give rise to the observed trans...

  18. Fluoride, bifluoride and trifluoromethyl complexes of iridium(I) and rhodium(I)


    Truscott, Byron; Nahra, Fady; Slawin, Alexandra Martha Zoya; Cordes, David Bradford; Nolan, Steven Patrick


    The ERC (Advanced Researcher Award FUNCAT to SPN), the EPSRC and Sasol (Stipend to BJT) are gratefully acknowledged for support. Herein we report robust methods for the preparation and full characterisation of a range of Ir(I) and Rh(I) fluoride and bifluoride complexes using N-heterocyclic carbenes (NHCs) as ancillary ligands. The processes that link the fluoride and the bifluoride species are investigated and reports of the first Ir–bifluoride and Ir(I)–NHC and Rh(I)–NHC trifluoromethyl ...

  19. Fluoride, bifluoride and trifluoromethyl complexes of iridium(I) and rhodium(I). (United States)

    Truscott, Byron J; Nahra, Fady; Slawin, Alexandra M Z; Cordes, David B; Nolan, Steven P


    Herein we report robust methods for the preparation and full characterisation of a range of Ir(I) and Rh(I) fluoride and bifluoride complexes using N-heterocyclic carbenes (NHCs) as ancillary ligands. The processes that link the fluoride and the bifluoride species are investigated and reports of the first Ir-bifluoride and Ir(I)-NHC and Rh(I)-NHC trifluoromethyl complexes are revealed.


    Directory of Open Access Journals (Sweden)

    Volodymyr Kharchenko


    Full Text Available For modelling of ADS-B messages transmitting on the base of low-orbit satellite constellation Іrіdіum the model of a communication channel “Aircraft - Satellite - Ground Station” was built using MATLAB Sіmulіnk. This model allowed to investigate dependences of the Bit Error Rate on a type of  signal coding/decoding, ratio Eb/N0 and satellite repeater gain

  1. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto


    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  2. Ruthenium(II) and iridium(III) complexes featuring NHC-sulfonate chelate. (United States)

    Rajaraman, A; Sahoo, A R; Hild, F; Fischmeister, C; Achard, M; Bruneau, C


    Three new complexes bearing a chelating (κ(2)C,O) NHC-SO3 ligand have been prepared. An original method for the synthesis of the imidazolium-sulfonate NHC precursor is described. The 5-membered ruthena- and irida-cycle containing complexes were fully characterized and evaluated in a series of catalytic transformations involving hydrogen auto-transfer processes.

  3. Imaging spin filter for electrons based on specular reflection from iridium (001)

    Energy Technology Data Exchange (ETDEWEB)

    Kutnyakhov, D.; Lushchyk, P. [Johannes Gutenberg-Universität, Institut für Physik, 55099 Mainz (Germany); Fognini, A.; Perriard, D. [Laboratorium für Festkörperphysik, ETH Zürich, 8093 Zürich (Switzerland); Kolbe, M.; Medjanik, K.; Fedchenko, E.; Nepijko, S.A.; Elmers, H.J. [Johannes Gutenberg-Universität, Institut für Physik, 55099 Mainz (Germany); Salvatella, G.; Stieger, C.; Gort, R.; Bähler, T.; Michlmayer, T.; Acremann, Y.; Vaterlaus, A. [Laboratorium für Festkörperphysik, ETH Zürich, 8093 Zürich (Switzerland); Giebels, F.; Gollisch, H.; Feder, R. [Universität Duisburg-Essen, Theoretische Festkörperphysik, 47057 Duisburg (Germany); Tusche, C. [Max Planck-Institut für Mikrostrukturphysik, 06120 Halle (Germany); and others


    As Stern–Gerlach type spin filters do not work with electrons, spin analysis of electron beams is accomplished by spin-dependent scattering processes based on spin–orbit or exchange interaction. Existing polarimeters are single-channel devices characterized by an inherently low figure of merit (FoM) of typically 10{sup −4}–10{sup −3}. This single-channel approach is not compatible with parallel imaging microscopes and also not with modern electron spectrometers that acquire a certain energy and angular interval simultaneously. We present a novel type of polarimeter that can transport a full image by making use of k-parallel conservation in low-energy electron diffraction. We studied specular reflection from Ir (001) because this spin-filter crystal provides a high analyzing power combined with a “lifetime” in UHV of a full day. One good working point is centered at 39 eV scattering energy with a broad maximum of 5 eV usable width. A second one at about 10 eV shows a narrower profile but much higher FoM. A relativistic layer-KKR SPLEED calculation shows good agreement with measurements. - Highlights: • Novel type of spin polarimeter can transport a full image by making use of k{sup →}{sub ||} conservation in LEED. • When combined with a hemispherical analyzer, it acquires a certain energy and angular interval simultaneously. • Ir (001) based spin-filter provides a high analyzing power combined with a “lifetime” in UHV of a full day. • Parallel spin detection improves spin polarimeter efficiency by orders of magnitude. • A relativistic layer-KKR SPLEED calculation shows good agreement with measurements.

  4. Osmium-Iridium Correlation and Osmium Isotopic Composition in Some Geological Boundaries and Meteorites (United States)

    Liu, Y. Z.; Wang, J. X.; Mao, X. Y.; Chai, C. F.


    Since the pioneering study of Alvarez et al. on K/T boundary event, Ir has long been considered to be the main indicator of extraterrestrial materials in boundaries, while little work about Os and its isotopic composition have been done. In this work a sophisticated radiochemical separation procedure together with neutron activation analsis (NAA) method was established for the determination of Os in some geological boundaries (P epsilon/epsilon, K/T, D/C, O/S, P/T). Combined with our early work--determination of Ir abundances [1], the sources of boundary events were deciphered by using the Os/Ir ratios. Simultaneously ^184Os/^190Os ratios in K/T boundaries, as well as inclusions of Allende chondrite and acid-insoluble residues of iron meteorites (Nandan, Jianshi, Longchang) were determined to search for the Os isotopic composition anomalies resulted from the extrasolar components by RNAA. The results show that the Os abundances exhibit a positive correlation with the Ir abundances for overall K/T boundary samples, but only the Os/Ir ratios of K/T boundaries, with the average of 0.98 +- 0.55, are in excellent agreement with 1.01 of the solar system [2], Accordingly, it provides new evidence for an extraterrestrial source of the K/T event. The results of ^184Os/^190Os ratios, with uncertainties of less than 1%, indicate there is no remarkable ^184Os/^190Os ratio anomaly in the K/T boundary samples, which implies the impacting matter may be from the solar system not the extrasolar, while no anomaly exists in the inclusions of Allende chondrite and acid-insoluble residues of iron meteorites, which disagree with the results obtained by Goel [3]. REFERENCES [1] Chai Chifang (1988) Isotopenpraxis 24, pp. 257-272. [2] Anders E. and Grevesse N. (l989) Geochim. Cosmochim. Acta 53, 197-214. [3] Goel P.S.(1987) Proc. Indian Acad. Sci. (Earth Planet. Sci), 96, pp. 81-102.

  5. Iridium abundance measurements across bio-event horizons in the fossil record

    Energy Technology Data Exchange (ETDEWEB)

    Orth, C.J.; Attrep, M. Jr.; Quintana, L.R. (Los Alamos National Lab., NM (USA))


    Geochemical measurements have been performed on thousands of rock samples collected across bio-event horizons using Instrumental Neutron Activation Analysis (INAA) for about 40 common and trace elements and radiochemical isolation procedures for Ir. On selected samples, Os, Pt and Au were also radiochemically determined. These studies have encompassed the time interval from the Precambrian-Cambrian transition to the Late Eocene impact (microspherule) horizons. Our early work strengthened the Alvarez impact hypothesis by finding the Ir (PGE) anomaly at the K-T boundary in continental sedimentary sequences. In collaborations with paleontologists, weak to moderately string Ir anomalies have been discovered at the Frasnian-Famennian boundary in Australia, in the Early Mississippian of Oklahoma, at the Mississipian-Pennsylvanian boundary of Oklahoma and Texas, and in the Late Cenomanian throughout the western interior of North America and on the south coast of England to date. We have found no compelling evidence for an impact related cause for these anomalies although PGE impact signatures in the two Late Cenomanian anomalies could be masked by the strong terrestrial mafic to ultramafic overprint. Thus far, our evidence for extinction events older than the terminal Cretaceous does not support recent hypotheses which suggest that impacts from cyclic swarms of comets in the inner Solar system were responsible for the periodic mass extinctions. 50 refs., 7 figs., 3 tabs.

  6. Numerical Simulation on Temperature Field of TIG Welding for Iridium-tungsten Alloy

    Institute of Scientific and Technical Information of China (English)

    LUO; Hong-yi; TANG; Xian; QIN; Shao-peng; LIU; Guo-hui; MA; Hui-min


    Ir-W alloy had the advantages of high temperature resistance,corrosion resistance,high hardness The clads produced with Ir-W alloy were sealed with TIG welding.According to energy conservation principle and characteristics of TIG welding,the numerical model of non-steady TIG welding pool shape under moving arc was established.By introducing the heat enthalpy and Gauss heat model of surface

  7. 76 FR 46313 - Notice of Issuance of Final Determination Concerning Iridium Satellite Telephones (United States)


    ... use distinct from that of the article or articles from which it was so transformed. See also 19 C.F.R... programming. This physical alteration, not visible to the naked eye, could be discerned by electronic testing... distinguishable fact from HQ 557208 and NY R02686. See Belcrest Linens supra. As a result, in Scenario I we find...

  8. Interplay of Wrinkles, Strain, and Lattice Parameter in Graphene on Iridium

    NARCIS (Netherlands)

    Hattab, H.; N'diaye, A.T.; Wall, D; Klein, C.; Jnawali, G.; Coraux, J; Busse, C; Gastel, van R.; Poelsema, B.; Michely, T.; Meyer-zu-Heringdorf, F.J.; Horn-von-Hoegen, M.


    Following graphene growth by thermal decomposition of ethylene on Ir(111) at high temperatures we analyzed the strain state and the wrinkle formation kinetics as function of temperature. Using the moiré spot separation in a low energy electron diffraction pattern as a magnifying mechanism for the di

  9. Investigation of aging processes of graphite tubes modified with iridium and rhodium used for atomic spectrometry (United States)

    Bulska, Ewa; Piaścik, Marek; Katskov, Dmitri; Darangwa, Nicholas; Grotti, Marco


    UV spectrometry (187-380 nm) with charge coupled device (CCD) detection was used to study the evolution of absorption spectra during the vaporization of various species in the pyrocoated graphite furnace, with electrodeposited Ir and Rh as modifiers. In order to mimic a typical matrix composition, various salts of aluminum, manganese, copper, magnesium, sodium, and lead were used in microgram amounts. Changes in spectra and vapor release rate, along with aging of the tubes in the repetitive temperature cycles, were observed. Compared to the unmodified pyrocoated tubes, the presence of Ir or Rh causes a significant reduction in the vaporization efficiency, especially for microgram amounts of copper and aluminum introduced as nitrates, and manganese introduced as a sulfate. The vaporization efficiency, for magnesium and sodium as chlorides, and for lead as a sulfate, remained unchanged. Interestingly, the aging of the tubes was accompanied by partial restoration of the spectral characteristics for unmodified tubes. For example, with unmodified pyrocoated tubes, the vaporization spectrum, appearing as a consequence of the decomposition of aluminum nitrate, consisted of Al2O bands overlapped by Al atomic lines. In the freshly modified tubes, intensities of those lines and bands were substantially reduced, and in this case, the dominance of AlO molecules was observed. The efficiency of vaporization of aluminum species increased in the aged modified tubes. The scanning electron microscopy (SEM) images of the modified surfaces for the new and aged tubes indicated that aging of the tubes is accompanied by the destruction of the pyrocoating, formation of pyrographite shells around the areas where the modifier was electrodeposited, and finally, complete substitution of the metal on the graphite surface by pyrographite debris.

  10. Bifunctional Catalysis: Direct Reductive Amination of Aliphatic Ketones with an Iridium-Phosphate Catalyst

    Directory of Open Access Journals (Sweden)

    Barbara Villa-Marcos


    Full Text Available Chiral amines are one of the ubiquitous functional groups in fine chemical, pharmaceutical and agrochemical products, and the most convenient, economical, and eco-benign synthetic pathway to these amines is direct asymmetric reductive amination (DARA of prochiral ketones. This paper shows that a wide range of aliphatic ketones can be directly aminated under hydrogenation conditions, affording chiral amines with good to excellent yields and with enantioselectivities up to 96% ee. The catalysis is effected by the cooperative action of a cationic Cp*Ir(III complex and its phosphate counteranion.

  11. Iridium-catalyzed [2 + 2 + 2] cycloaddition of α,ω-diynes with nitriles. (United States)

    Onodera, Gen; Shimizu, Yoshihisa; Kimura, Jun-na; Kobayashi, Junya; Ebihara, Yukiko; Kondo, Kei; Sakata, Ken; Takeuchi, Ryo


    [Ir(cod)Cl](2)/DPPF or BINAP efficiently catalyzed the cycloaddition of α,ω-diynes with nitriles to give pyridines. The reaction can accommodate a very wide range of nitriles. Both aliphatic and aromatic nitriles smoothly reacted with α,ω-diynes to give pyridines. Ten equivalents of unactivated aliphatic nitrile were enough to give the product in high yield. Aliphatic nitriles bearing an acetal or amino moiety could be used for the reaction. The highly regioselective cycloaddition of unsymmetrical diyne bearing two different internal alkyne moieties was achieved. The observed regioselectivity could be reasonably explained by considering the different reactivities of the α-position in iridacyclopentadiene. Regioselective cycloaddition was successfully applied to the synthesis of terpyridine and quinquepyridine. This chemistry was extended to a new and efficient synthesis of oligoheteroarenes. Five aromatic or heteroaromatic rings were connected in a single operation. [Ir(cod)Cl](2)/chiral diphosphine catalyst can be applied to enantioselective synthesis. Kinetic resolution of the racemic secondary benzyl nitrile catalyzed by [Ir(cod)Cl](2)/SEGPHOS gave a central carbon chiral pyridine in 80% ee. The mechanism was analyzed on the basis of the B3LYP level of density functional calculations.

  12. Mitochondrial Dynamics Tracking with Two-Photon Phosphorescent Terpyridyl Iridium(III) Complexes (United States)

    Huang, Huaiyi; Zhang, Pingyu; Qiu, Kangqiang; Huang, Juanjuan; Chen, Yu; Ji, Liangnian; Chao, Hui


    Mitochondrial dynamics, including fission and fusion, control the morphology and function of mitochondria, and disruption of mitochondrial dynamics leads to Parkinson’s disease, Alzheimer’s disease, metabolic diseases, and cancers. Currently, many types of commercial mitochondria probes are available, but high excitation energy and low photo-stability render them unsuitable for tracking mitochondrial dynamics in living cells. Therefore, mitochondrial targeting agents that exhibit superior anti-photo-bleaching ability, deep tissue penetration and intrinsically high three-dimensional resolutions are urgently needed. Two-photon-excited compounds that use low-energy near-infrared excitation lasers have emerged as non-invasive tools for cell imaging. In this work, terpyridyl cyclometalated Ir(III) complexes (Ir1-Ir3) are demonstrated as one- and two-photon phosphorescent probes for real-time imaging and tracking of mitochondrial morphology changes in living cells.

  13. Iridium-Catalyzed Dynamic Kinetic Isomerization: Expedient Synthesis of Carbohydrates from Achmatowicz Rearrangement Products. (United States)

    Wang, Hao-Yuan; Yang, Ka; Bennett, Scott R; Guo, Sheng-rong; Tang, Weiping


    A highly stereoselective dynamic kinetic isomerization of Achmatowicz rearrangement products was discovered. This new internal redox isomerization provided ready access to key intermediates for the enantio- and diastereoselective synthesis of a series of naturally occurring sugars. The nature of the de novo synthesis also enables the preparation of both enantiomers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis and Reactivity of Iron-Iridium Heterobimetallic Complexes Using Tridentate Phosphine Ligands


    Nawar, N. [نجوى نوار


    Treatment of {Fe (CO)3 {(PPh2) 2 C=CH2}] with PPh2H gives the addition product [Fe (CO)3 {(PPh2) 2 CHCH2 PPh2}] (1). The uncoordinated phosphine group of complex 1 reacts with Ir4 (CO)12 to give mono-, di- and tri-substituted heterobimetallic cluster complexes. درس تفاعل المتراكب [} C0)3 Fe {(PPh2)2 C=CH2)] مع ثنائي فينيل الفوسفين وفق تفاعل مايكل للإضافة . ‏وقد استخدمت المتراكبات الناتجة في تحضير متراكبات ثنائية الفلز غير المتجانس . وقد أظهرت الدراسة أن مجموعة الفوسفين غير المرتبطة في ...

  15. Electrodeposition of Iridium Oxide by Cyclic Voltammetry: Application of Response Surface Methodology

    Directory of Open Access Journals (Sweden)

    Kakooei Saeid


    Full Text Available The effects of scan rate, temperature, and number of cycles on the coating thickness of IrOX electrodeposited on a stainless steel substrate by cyclic voltammetry were investigated in a statistical system. The central composite design, combined with response surface methodology, was used to study condition of electrodeposition. All fabricated electrodes were characterized using electrochemical methods. Field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy were performed for IrOX film characterization. Results showed that scan rate significantly affects the thickness of the electrodeposited layer. Also, the number of cycles has a greater effect than temperature on the IrOX thickness.

  16. Peptide-Functionalized Luminescent Iridium Complexes for Lifetime Imaging of CXCR4 Expression

    NARCIS (Netherlands)

    Kuil, J.; Steunenberg, P.; Chin, P.T.K.; Oldenburg, J.; Jalink, K.; Velders, A.H.; Leeuwen, F.W.B. van


    The chemokine receptor 4 (CXCR4) is over-expressed in 23 types of cancer in which it plays a role in, among others, the metastatic spread. For this reason it is a potential biomarker for the field of diagnostic oncology. The antagonistic Ac-TZ14011 peptide, which binds to CXCR4, has been conjugated

  17. Titanium-iridium oxide layer coating to suppress photocorrosion during photocatalytic water splitting

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Yongwoo; Lee, Hyunjoo [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of); Kwon, Yongwoo; Lee, Hyunjoo [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of)


    Photocatalysts with a small band gap energy have received a great deal of interest due their high solar conversion efficiencies. Cuprous oxide (Cu{sub 2}O) has attracted attention because of its small bandgap energy, a direct bandgap structure, its suitable band structure for water splitting, high absorption coefficient, non-toxicity, and its large abundance. However, it has poor stability due to the fickle oxidation states of copper. To enhance the stability and the production rate of hydrogen and oxygen, a TiIrOX overlayer was successfully formed on the Cu{sub 2}O under various synthesis conditions. The composition and oxidation state of the Ir species in the overlayer were optimized through the control of the Ir precursor and the amount of water. The Ir/Ti precursor molar ratio was linearly related to the surface Ir/Ti molar ratio. The addition of water converted the Ir precursor to IrO{sub 2}. The thickness of the overlayer was controlled by differing the synthesis times of the coating. Then, the largest amounts of hydrogen and oxygen were produced through the optimization of the TiIrOX overlayer with a higher IrO{sub 2} fraction and a thicker overlayer.

  18. A Performance Analysis of the IRIDIUM Low Earth Orbit Satellite System (United States)


    Melbourne 144.97 -37.80 0.00 Kansas City -94.59 39.13 0.23 Dhahran 50.00 27.00 0.76 Beijing 116.47 39.90 0.18 Berlin 13.42 52.53 0.03 Capetown ... Capetown 0.143 0.167 0.167 0.167 0.167 0.167 0.167 0 An actual communications network is not likely to have a uniform traffic distribution. In this...0.167 0.167 0.167 0.167 0 0.167 0.167 Berlin 0.100 0.167 0.167 0.167 0.167 0.167 0 0.167 . Capetown 0.100 0.167 0.167 0.167 0.167 0.167 0.167 0 In

  19. The gold button technique for intraoral interstitial implants with iridium-192 seeds. (United States)

    Kumar, P P; Henschke, U K


    The higher the radiation dose, the better is tumor control. High tumor doses are feasible only by interstitial irradiation. To achieve uniform dose distribution throughout the area or volume of implant, one has to use established distribution rules. In straight tube technique we have to use heavy endloading to compensate for uncrossed ends. In implants for intraoral lesions, heavy endloading gives a high dose to the opposing normal mucosa. The new gold button technique considerably reduces the dose to the normal mucosa, thus minimizing the morbidity.

  20. Five years' experience with the gold button technique for intraoral interstitial implants with iridium-192 seeds. (United States)

    Kumar, P P; Henschke, U K


    To simulate crossing of the ends in standard removable interstitial implants, we used the loop technique for intraoral tumors when treating them with afterloading interstitial removable implants. Because of technical problems, we changed to a straight tube method with heavy end-loading to compensate for the uncrossed ends. High doses to the normal mucosa close to heavy end-loading is reduced 2.5 times by the use of gold buttons in place of standard stainless steel buttons, thus decreasing unnecessary mucosal reactions and morbidity.

  1. Manipulation of phosphorescence efficiency of cyclometalated iridium complexes by substituted o-carboranes. (United States)

    Lee, Young Hoon; Park, Jihyun; Jo, Song-Jin; Kim, Miyoung; Lee, Junseong; Lee, Sang Uck; Lee, Min Hyung


    A series of [(C^N)2 Ir(acac)] complexes [{5-(2-R-CB)ppy}2 Ir(acac)] (3 a-3 g; acac=acetylacetonate, CB=o-carboran-1-yl, ppy=2-phenylpyridine; R=H (3 a), Me (3 b), iPr (3 c), iBu (3 d), Ph (3 e), CF3 C6 H4 (3 f), C6 F5 (3 g)) with various 2-R-substituted o-carboranes at the 5-position in the phenyl ring of the ppy ligand were prepared. X-ray diffraction studies revealed that the carboranyl CC bond length increases with increasing steric and electron-withdrawing effects from the 2-R substituents. Although the absorption and emission wavelengths of the complexes are almost invariant to the change of 2-R group, the phosphorescence quantum efficiency varies from highly emissive (ΦPL ≈0.80 for R=H, alkyl) to poorly emissive (R=aryl) depending on the 2-R group and the polarity of the medium. Theoretical studies suggest that 1) the almost nonemissive nature of the 2-aryl-substituted complexes is mainly attributable to the large contribution to the LUMO in the S1 excited state from an o-carborane unit and 2) the variation in the CC bond length between the S0 and T1 state structures increases with increasing steric (2-alkyl) and electronic effects (2-aryl) of the 2-R substituent and the polarity of the solvent. The solution-processed electroluminescence (EL) devices that incorporated 3 b and 3 d as emitters displayed higher performance than the device based on the parent [(ppy)2 Ir(acac)] complex. Along with the high phosphorescence efficiency, the bulkiness of the 2-R-o-carborane unit is shown to play an important role in improving device performance.

  2. Iridium- and Ruthenium-Catalyzed N-alkylation of Amines with Alcohols and Amines

    DEFF Research Database (Denmark)

    Lorentz-Petersen, Linda Luise Reeh

    via folding assisted ligation. One segment was synthesised as the C-terminal thioester by Boc-SPPS and the other segment as a C-terminal acid by Fmoc-SPPS. The sites of mutation were all in the α-helical region of the protein and the mutation choices were alanine and Aib, which both posses a high α...... is environmentally benign as it is performed in the absence of both solvent and additives and the only by-product is ammonia. Additionally, the work-up procedure is a simple distillation of the product directly from the reaction mixture. Synthesis of piperazines In the Madsen group it has previously been...... catalysts have been employed for the N-alkylation of amines with either alcohols or amines. Synthesis of secondary amines Self-condensation of primary amines afforded secondary amines in good to high yields. The reaction is catalyzed by the commercially available [Cp*IrCl2]2 complex. The procedure...

  3. Literature Review: Weldability of Iridium DOP-26 Alloy for General Purpose Heat Source

    Energy Technology Data Exchange (ETDEWEB)

    Burgardt, Paul [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Pierce, Stanley W. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


    The basic purpose of this paper is to provide a literature review relative to fabrication of the General Purpose Heat Source (GPHS) that is used to provide electrical power for deep space missions of NASA. The particular fabrication operation to be addressed here is arc welding of the GPHS encapsulation. A considerable effort was made to optimize the fabrication of the fuel pellets and of other elements of the encapsulation; that work will not be directly addressed in this paper. This report consists of three basic sections: 1) a brief description of the GPHS will be provided as background information for the reader; 2) mechanical properties and the optimization thereof as relevant to welding will be discussed; 3) a review of the arc welding process development and optimization will be presented. Since the welding equipment must be upgraded for future production, some discussion of the historical establishment of relevant welding variables and possible changes thereto will also be discussed.

  4. Efficient white organic light-emitting diodes based on iridium complex sensitized copper complex

    Energy Technology Data Exchange (ETDEWEB)

    Su Zisheng; Li Wenlian; Chu Bei; Xu Maoliang; Che Guangbo; Wang Dan; Han Liangliang; Li Xiao; Zhang Dongyu; Bi Defeng; Chen Yiren [Key Laboratory of Excited State Processes, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, Changchun 130033 (China)], E-mail:


    Efficient double emission-layer white organic light-emitting diodes comprising a yellow emission from bis[(4,6-difluorophenyl)-pyridinato-N,C{sup 2}](picolinato)Ir(III) (FIrpic) sensitized [Cu(bis[2-(diphenylphosphino)phenyl]ether) (6,7-Dicyanodipyrido[2,2-d : 2', 3'-f] quinoxaline)]BF{sub 4}(Cu{sup I} complex) and a blue emission from 4, 4'-bis(2,2'-diphenylvinyl)-1, 1'-biphenyl (DPVBi) were demonstrated. The emission spectrum can be fine tuned by effectively controlling the thicknesses of the two emission layers. The optimized device with 18 nm FIrpic and the Cu{sup I} complex codoped 4, 4'-N,N'-dicarbazole-biphenyl layer and 12 nm DPVBi layer shows a maximum current efficiency of 8.5 cd A{sup -1}, a maximum power efficiency of 5.3 lm W{sup -1} and a maximum luminance of 3290 cd m{sup -2}. Moreover, the device exhibits a CIE coordinate of (0.345, 0.357) at a bias of 8 V and a slight colour variation with increased voltage from 6 to 16 V.

  5. Reductive Cleavage of CO2 by Metal-Ligand-Cooperation Mediated by an Iridium Pincer Complex. (United States)

    Feller, Moran; Gellrich, Urs; Anaby, Aviel; Diskin-Posner, Yael; Milstein, David


    A unique mode of stoichiometric CO2 activation and reductive splitting based on metal-ligand-cooperation is described. The novel Ir hydride complexes [((t)Bu-PNP*)Ir(H)2] (2) ((t)Bu-PNP*, deprotonated (t)Bu-PNP ligand) and [((t)Bu-PNP)Ir(H)] (3) react with CO2 to give the dearomatized complex [((t)Bu-PNP*)Ir(CO)] (4) and water. Mechanistic studies have identified an adduct in which CO2 is bound to the ligand and metal, [((t)Bu-PNP-COO)Ir(H)2] (5), and a di-CO2 iridacycle [((t)Bu-PNP)Ir(H)(C2O4-κC,O)] (6). DFT calculations confirm the formation of 5 and 6 as reversibly formed side products, and suggest an η(1)-CO2 intermediate leading to the thermodynamic product 4. The calculations support a metal-ligand-cooperation pathway in which an internal deprotonation of the benzylic position by the η(1)-CO2 ligand leads to a carboxylate intermediate, which further reacts with the hydride ligand to give complex 4 and water.

  6. Seven-coordinate iridium(V) polyhydrides with chelating bis(silyl) ligands

    Energy Technology Data Exchange (ETDEWEB)

    Loza, M.; Faller, J.W.; Crabtree, R.H. [Yale Univ., New Haven, CT (United States)


    The pentahydride IrH{sub 5}(PPh{sub 3}){sub 2} reacts with chelating silanes with loss of H{sub 2} to form the classical seven-coordinate distorted pentagonal bipyramidal silyl polyhydride complexes IrH{sub 3}(disil)(PPh{sub 3}){sub 2}(disil: dmsb, 3a; tids, 3b) with monodentate silanes to give IrH{sub 4}(SiR{sub 3})(PPh{sub 3}){sub 2} (R: Et, 4a; Ph, 4b) and with triphenyltin hydride to give IrH{sub 3{minus}} (SnPh{sub 3}){sup 2}(PPh{sub 3}){sub 2} (5), all rare examples of Ir(V). A crystal structure was obtained for 3a. Crystal data: orthorhombic; space group Pbca (No. 61); a = 17.1534(6) {Angstrom}; b = 25.688(2) {Angstrom}; c = 19.0641(9) {Angstrom}; V=8400(1) {Angstrom}{sup 3}; Z=8.

  7. Novel Charge Ordering in the Trimer Iridium Oxide BaIrO3

    Directory of Open Access Journals (Sweden)

    Ichiro Terasaki


    Full Text Available We have prepared polycrystalline samples of the trimer Ir oxide BaIrO3 with face-shared Ir3O12 trimers, and have investigated the origin of the phase transition at 182 K by measuring resistivity, thermopower, magnetization and synchrotron X-ray diffraction. We propose a possible electronic model and transition mechanism, starting from a localized electron picture on the basis of the Rietveld refinement. Within this model, BaIrO3 can be basically regarded as a Mott insulator, when the Ir3O12 trimer is identified to one pseudo-atom or one lattice site. The transition can be viewed as a transition from the Mott insulator phase to a kind of charge ordered insulator phase.

  8. Electronic structure, cohesive, and magnetic properties of the actinide-iridium Laves phases

    DEFF Research Database (Denmark)

    Eriksson, O.; Johansson, B.; Brooks, M. S. S.


    The electronic structure of the isostructural AIr2 systems (A=Th, Pa, U, Np, Pu, and Am) has been obtained by means of the scalar relativistic and fully relativistic linear muffin-tin orbital techniques. Ground-state properties such as lattice constants and onset of magnetic order have been calcu...

  9. Iridium concentration driving the mechanical properties of iridium–aluminum compounds

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Y. [School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500 (China); Wen, M. [State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals, Kunming 650106 (China); Wang, L.; Wang, X. [School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500 (China); Lin, Y.H., E-mail: [School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500 (China); Guan, W.M., E-mail: [State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals, Kunming 650106 (China)


    Using first-principles density functional theory approach, we systematically investigate the formation enthalpy, mechanical stability, elastic modulus, brittle or ductile behavior and electronic structure of Ir–Al compounds with different Ir concentrations. The calculated convex hull indicates that IrAl with CsCl-type structure is more stability than that of other Ir–Al compounds at ground state. We found that the resistance to volume deformation is related to the Ir concentration in Ir–Al compounds, while the bulk modulus of these compounds increases with increasing Ir concentrations. However, the Ir{sub 5}Al{sub 3} has the strongest shear deformation resistance and has the highest elastic stiffness in these Ir–Al compounds. The calculated theoretical hardness of Ir{sub 2}Al{sub 9} is bigger than other Ir–Al compounds. Ir{sub 2}Al{sub 3} and Ir{sub 2}Al{sub 9} exhibit brittle behavior in contrast to other Ir–Al compounds exhibit ductile behavior. This discrepancy is originated from the structural feature and localized hybridization between Ir and Al atoms. Finally, we conclude that alloying can change brittle behavior of metal Ir. - Highlights: • The correlation between Ir concentration and mechanical properties is studied. • The convex hull indicates that IrAl is the most stable structure. • We found that alloying can weaken the brittle behavior of metal Ir. • We found that the bulk modulus of Ir–Al compound is related to Ir concentration. • The theoretical hardness of Ir{sub 2}Al{sub 9} is higher than other Ir–Al compounds.

  10. High Surface Area Iridium Anodes and Melt Containers for Molten Oxide Electrolysis Project (United States)

    National Aeronautics and Space Administration — Direct electrochemical reduction of molten regolith is the most attractive method of oxygen production on the lunar surface, because no additional chemical reagents...

  11. Iridium double perovskite Sr2YIrO6 : A combined structural and specific heat study (United States)

    Corredor, L. T.; Aslan-Cansever, G.; Sturza, M.; Manna, Kaustuv; Maljuk, A.; Gass, S.; Dey, T.; Wolter, A. U. B.; Kataeva, Olga; Zimmermann, A.; Geyer, M.; Blum, C. G. F.; Wurmehl, S.; Büchner, B.


    Recently, the iridate double perovskite Sr2YIrO6 has attracted considerable attention due to the report of unexpected magnetism in this Ir5 + (5 d4 ) material, in which according to the Jeff model, a nonmagnetic ground state is expected. However, in recent works on polycrystalline samples of the series Ba2 -xSrxYIrO6 no indication of magnetic transitions have been found. We present a structural, magnetic, and thermodynamic characterization of Sr2YIrO6 single crystals, with emphasis on the temperature and magnetic field dependence of the specific heat. As determined by x-ray diffraction, the Sr2YIrO6 single crystals have a cubic structure, with space group F m 3 ¯m . In agreement with the expected nonmagnetic ground state of Ir5 + (5d 4 ) in Sr2YIrO6 , no magnetic transition is observed down to 430 mK. Moreover, our results suggest that the low-temperature anomaly observed in the specific heat is not related to the onset of long-range magnetic order. Instead, it is identified as a Schottky anomaly caused by paramagnetic impurities present in the sample, of the order of n ˜0.5 (2 )% . These impurities lead to non-negligible spin correlations, which nonetheless, are not associated with long-range magnetic ordering.

  12. Performance of a PEM water electrolyser using a TaC-supported iridium oxide electrocatalyst

    DEFF Research Database (Denmark)

    Polonský, J.; Mazúr, P.; Paidar, M.


    Polymer electrolyte membrane (PEM) water electrolysis is an attractive way of producing carbon-free hydrogen. One of the drawbacks of this method is the need for precious metal-based electrocatalysts. This calls for a highly efficient utilization of the precious metal, which can be obtained by di...

  13. CO2 capture and conversion with a multifunctional polyethyleneimine-tethered iminophosphine iridium catalyst/adsorbent. (United States)

    McNamara, Nicholas D; Hicks, Jason C


    Tunable, multifunctional materials able to capture CO2 and subsequently catalyze its conversion to formic acid were synthesized by the modification of branched polyethyleneimine (PEI) with an iminophosphine ligand coordinated to an Ir precatalyst. The molecular weight of the PEI backbone was an important component for material stability and catalytic activity, which were inversely related. The amine functionalities on PEI served three roles: 1) primary amines were used to tether the ligand and precatalyst, 2) amines were used to capture CO2 , and 3) amines served as a base for formate stabilization during catalysis. Ligand studies on imine and phosphine based ligands showed that a bidentate iminophosphine ligand resulted in the highest catalytic activity. X-ray photoelectron spectroscopy revealed that an increase in Ir 4f binding energy led to an increase in catalytic activity, which suggests that the electronics of the metal center play a significant role in catalysis. Catalyst loading studies revealed that there is a critical balance between free amines and ligand-metal sites that must be reached to optimize catalytic activity. Thus, it was found that the CO2 capture and conversion abilities of these materials could be optimized for reaction conditions by tuning the structure of the PEI-tethered materials.

  14. Electrocatalytic performances of N-doped graphene with anchored iridium species in oxygen reduction reaction (United States)

    Choi, Kwangrok; Lee, Seungjun; Shim, Yeonjun; Oh, Junghoon; Kim, Sujin; Park, Sungjin


    Development of new systems with high catalytic performances in the oxygen reduction reaction (ORR) for practical applications in fuel cells and metal-air batteries is a challenge. We develop a one-pot solution method for producing a novel hybrid material consisting of Ir species anchored on N-doped graphene. The hybrid is synthesized by reacting graphene oxide with IrCl3 · xH2O in dimethylformamide under reflux. Chemical and structural analyses confirm the attachment of Ir atoms to the N and O atoms of the N-doped graphene-based materials. The hybrid shows a good electrocatalytic performance for the ORR in alkaline media, with an onset potential of 0.88 V (versus the reversible hydrogen electrode), high long-term durability, and good tolerance for methanol poisoning.

  15. Iridium single atom tips fabricated by field assisted reactive gas etching (United States)

    Wood, John A.; Urban, Radovan; Salomons, Mark; Cloutier, Martin; Wolkow, Robert A.; Pitters, Jason L.


    We present a simple, reliable method to fabricate Ir single atom tips (SATs) from polycrystalline wire. An electrochemical etch in CaCl2 solution is followed by a field assisted reactive gas etch in vacuum at room temperature using oxygen as an etching gas and neon as an imaging gas. Once formed, SATs are cooled to liquid nitrogen temperatures and their underlying structure is examined through evaporation of the apex atoms. Furthermore, a method is developed to repair Ir SATs at liquid nitrogen temperatures when apex atoms evaporate. This method may be used to fabricate Ir SAT ion sources.

  16. Very strong antiferromagnetic interlayer exchange coupling with iridium spacer layer for perpendicular magnetic tunnel junctions (United States)

    Yakushiji, Kay; Sugihara, Atsushi; Fukushima, Akio; Kubota, Hitoshi; Yuasa, Shinji


    We systematically studied the interlayer exchange coupling (IEC) in a perpendicular synthetic antiferromagnetically coupled structure having an Ir spacer layer for perpendicular magnetic tunnel junctions (p-MTJs). We found a broader peak in IEC energy density (Jex) versus spacer thickness (tIr) compared with the case of using a Ru spacer. The highest IEC energy density was 2.6 erg/cm2 at a tIr of about 5 nm. The p-MTJ nanopillars had a high magnetoresistance ratio (131%) as well as a high spin-transfer torque (STT) switching efficiency (about 2). An Ir spacer can be used to make a stable reference layer for STT magnetoresistive random access memory.

  17. Nucleophilicity and P-C bond formation reactions of a terminal phosphanido iridium complex

    NARCIS (Netherlands)

    Serrano, Á.L.; Casado, M.A.; Ciriano, M.A.; de Bruin, B.; López, J.A.; Tejel, C.


    The diiridium complex [{Ir(ABPN(2))(CO)}(2)(μ-CO)] (1; [ABPN(2)]- = [(allyl)B(Pz)(2)(CH(2)PPh(2))]-) reacts with diphenylphosphane affording [Ir(ABPN(2))(CO)(H) (PPh(2))] (2), the product of the oxidative addition of the P-H bond to the metal. DFT studies revealed a large contribution of the

  18. Solid-state electrochemiluminescence of a novel iridium(Ⅲ) complex

    Institute of Scientific and Technical Information of China (English)


    The sofid-state ECL behavior of a water-insoluble bis-cyclometalated (pq)2Ir(N-phMA) complex is presented, in which pq is a 2-phenylquinoline anion and N-phMA is N-phenyl methacrylamide, a monoanionic bidentate ligand. The MWNTs/(pq)2Ir(N-phMA) film, MWNTs/Ru(bpy)32+ film and (pq)2Ir(N-phMA) directly modified glassy carbon electrode were fabricated; only the MWNTs/(pq)2Ir(N-phMA) film can produce steady ECL in the presence of tri-n-propylamine as a coreactant.

  19. Unusual NHC-Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes

    KAUST Repository

    Sipos, Gellért


    N-heterocyclic carbene (NHC) ligands with naphthyl side chains were employed for the synthesis of unsaturated, yet isolable [(NHC)Ir(cod)]+ (cod=1,5-cyclooctadiene) complexes. These compounds are stabilised by an interaction of the aromatic wingtip that leads to a sideways tilt of the NHC-Ir bond. Detailed studies show how the tilting of such N-heterocyclic carbenes affects the electronic shielding properties of the carbene carbon atom and how this is reflected by significant upfield shifts in the 13CNMR signals. When employed in the intramolecular hydroamination, these [(NHC)Ir(cod)]+ species show very high catalytic activity under mild reaction conditions. An enantiopure version of the catalyst system produces pyrrolidines with excellent enantioselectivities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. The diastereoselective synthesis of octahedral cationic iridium hydride complexes with a stereogenic metal centre. (United States)

    Humbert, Nicolas; Mazet, Clément


    We report herein the highly diastereoselective synthesis of octahedral cationic Ir(iii) hydride complexes with a stereogenic metal centre following various strategies. The configurational stability of these compounds has also been investigated.


    Page, Norman J; Talkington, Raymond W.


    Samples of spinel lherzolite, harzburgite, dunite, and chromitite from the Bay of Islands, Lewis Hills, Table Mountain, Advocate, North Arm Mountain, White Hills Periodite Point Rousse, Great Bend and Betts Cove ophiolite complexes in Newfoundland were analyzed for the platinum-group elements (PGE) Pd, Pt, Rh, Ru and Ir. The ranges of concentration (in ppb) observed for all rocks are: less than 0. 5 to 77 (Pd), less than 1 to 120 (Pt), less than 0. 5 to 20 (Rh), less than 100 to 250 (Ru) and less than 20 to 83 (Ir). Chondrite-normalized PGE ratios suggest differences between rock types and between complexes. Samples of chromitite and dunite show relative enrichment in Ru and Ir and relative depletion in Pt and Pd.

  2. Anion–Anion Bonding and Topology in Ternary Iridium Seleno–Stannides

    Energy Technology Data Exchange (ETDEWEB)

    Trump, Benjamin A.; Tutmaher, Jake A.; McQueen, Tyrel M. (JHU)


    The synthesis and physical properties of two new and one known Ir–Sn–Se compound are reported. Their crystal structures are elucidated with transmission electron microscopy and powder X-ray diffraction. IrSn0.45Se1.55 is a pyrite phase which consists of tilted corner-sharing IrX6 octahedra with randomly distributed (Sn–Se)4– and (Se–Se)2– dimers. Ir2Sn3Se3 is a known trigonally distorted skutterudite that consists of cooperatively tilted corner-sharing IrSn3Se3 octahedra with ordered (Sn–Se)24– tetramers. Ir2SnSe5 is a layered, distorted β-MnO2 (pyrolusite) structure consisting of a double IrSe6 octrahedral row, corner sharing in the a direction and edge sharing in the b direction. This distorted pyrolusite contains (Se–Se)2– dimers and Se2– anions, and each double row is “capped” with a (Sn–Se)n polymeric chain. Resistivity, specific heat, and magnetization measurements show that all three have insulating and diamagnetic behavior, indicative of low-spin 5d6 Ir3+. Electronic structure calculations on Ir2Sn3Se3 show a single, spherical, nonspin–orbit split valence band and suggest that Ir2Sn3Se3 is topologically nontrivial under tensile strain due to inversion of Ir-d and Se-p states.

  3. Computationally Probing the Performance of Hybrid, Heterogeneous, and Homogeneous Iridium-Based Catalysts for Water Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    García-Melchor, Max [SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA (United States); Vilella, Laia [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST),Tarragona (Spain); Departament de Quimica, Universitat Autonoma de Barcelona, Barcelona (Spain); López, Núria [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Vojvodic, Aleksandra [SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park CA (United States)


    An attractive strategy to improve the performance of water oxidation catalysts would be to anchor a homogeneous molecular catalyst on a heterogeneous solid surface to create a hybrid catalyst. The idea of this combined system is to take advantage of the individual properties of each of the two catalyst components. We use Density Functional Theory to determine the stability and activity of a model hybrid water oxidation catalyst consisting of a dimeric Ir complex attached on the IrO2(110) surface through two oxygen atoms. We find that homogeneous catalysts can be bound to its matrix oxide without losing significant activity. Hence, designing hybrid systems that benefit from both the high tunability of activity of homogeneous catalysts and the stability of heterogeneous systems seems feasible.

  4. Water oxidation with molecularly defined iridium complexes: insights into homogeneous versus heterogeneous catalysis. (United States)

    Junge, Henrik; Marquet, Nicolas; Kammer, Anja; Denurra, Stefania; Bauer, Matthias; Wohlrab, Sebastian; Gärtner, Felix; Pohl, Marga-Martina; Spannenberg, Anke; Gladiali, Serafino; Beller, Matthias


    Molecularly defined Ir complexes and different samples of supported IrO(2) nanoparticles have been tested and compared in the catalytic water oxidation with cerium ammonium nitrate (CAN) as the oxidant. By comparing the activity of nano-scaled supported IrO(2) particles to the one of organometallic complexes it is shown that the overall activity of the homogeneous Ir precursors is defined by both the formation of the homogeneous active species and its conversion to Ir(IV)-oxo nanoparticles. In the first phase of the reaction the activity is dominated by the homogeneous active species. With increasing reaction time, the influence of nano-sized Ir-oxo particles becomes more evident. Notably, the different conversion rates of the homogeneous precursor into the active species as well as the conversion into Ir-oxo nanoparticles and the different particle sizes have a significant influence on the overall activity. In addition to the homogeneous systems, IrO(2)@MCM-41 has also been synthesized, which contains stabilized nanoparticles of between 1 and 3 nm in size. This latter system shows a similar activity to IrCl(3)⋅xH(2)O and complexes 4 and 5. Mechanistic insights were obtained by in situ X-ray absorption spectroscopy and scanning transmission electron microscopy.

  5. beta-acylvinyl anion and dianion equivalents: lithiation of 1-[(2EZ)-3-chloroprop-2-enyl]-1H-1,2,3-benzotriazole: preparation and elaboration of 1-(2-oxiranylvinyl)-1H-benzotriazoles. (United States)

    Katritzky, Alan R; Manju, Kavita; Gromova, Anna V; Steel, Peter J


    The allyllithium generated from 1-[(2EZ)-3-chloroprop-2-enyl]-1H-1,2,3-benzotriazole (5) and LDA, in the presence of HMPA, reacts with enolizable and nonenolizable carbonyls solely at the CCl terminus to give 1-(2-oxiranylvinyl)benzotriazoles 6a-g in 61-82% yields. Allyllithiums generated from 6a,c reacted exclusively at the CBt terminus to give 10a-d in 68-88% yields. Acidic hydrolysis of (oxiranylvinyl)benzotriazoles 6a-g and 10a-d provided 4-hydroxyalk-2-en-1-one derivatives 12a,b,c,e,g, 13a-d, and furan 14 in 54-86% yields.

  6. Exploring the microscopic solvation of doubly charged anions: symmetric or asymmetric solvation in the CO 2-(CH 2) 4-CO 22-·(H 2O) 2 dicarboxylate dianion cluster? (United States)

    Dessent, Caroline E. H.; Rigby, Christopher


    Optimised geometries and absolute energies of CO 2-(CH 2) 4-CO 22-·(H 2O) n, n=0,1,2, were determined using density functional methods. The n=1 global minimum was found to contain a bifurcated hydrogen-bond, with the n=2 minimum containing two such bonds. Vertical detachment energies (VDEs) obtained for the n=1,2 global minima at the MP2/6-31+G*//B3LYP/6-31+G* level agree well with experiment, and suggest that the two waters solvate the carboxylate groups separately in CO 2-(CH 2) 4-CO 22-·(H 2O) 2. However, a number of different isomers were identified for both clusters with several isomers producing similar VDEs, indicating that the measured VDEs may contain contributions from multiple isomers. Calculations are presented illustrating that IR predissociation spectra would allow the direct identification of these isomers.

  7. IrII(ethene): metal or carbon radical? Part II: oxygenation via iridium or direct oxygenation at ethene? (United States)

    Hetterscheid, Dennis G H; Bens, Mariska; de Bruin, Bas


    Treatment of [(Me3tpa)IrII(ethene)]2+ (Me(3)tpa =N,N,N-tri(6-methyl-2-pyridylmethyl)amine)(1(2+)) with dioxygen in weakly coordinating solvents results in formation of [(Me3tpa)IrIII(ethene)(superoxo)]2+ (4a2+). In the presence of DMPO (DMPO = 5,5-dimethyl-2-pyrrolidine-1-oxide) DMPO is substituted for ethene, and subsequently oxidized to DMPOX by the superoxo fragment to give [(Me3tpa)IrIII(DMPOX)]2+ (7(2+); DMPOX = 5,5-dimethyl-2-pyrrolidone-1-oxide). In acetonitrile, in the absence of DMPO, oxygenation of 1(2+) to [(Me3tpa)IrIII(formylmethyl)(MeCN)]2+ (2(2+)) is observed. In the presence of DMPO the formation of 2(2+) and 7(2+) is competing. Oxygenation of 1(2+) to 2(2+) may proceed via 4a(2+), involving an insertion mechanism at the metal. However, a mechanism based on olefin ligand non-innocence seems a reasonable alternative. This involves formation of acetonitrile adduct [(Me3tpa)Ir(ethene)(MeCN)]2+ (3(2+)), which has a significant metalla-ethyl radical (IrIII-CH2CH2*) character, allowing attack of 3O2 directly at the ethene ligand. Both pathways are discussed on the basis of experimental observations and DFT geometry optimizations.

  8. Identification of reactive oxygen species in iridium-based OER catalysts by in situ photoemission and absorption spectroscopy


    Pfeifer, V.


    A change in our energy supply from fossil fuels to intermittent renewables requires energy storage capacity. Part of this capacity may be delivered from chemical energy conversion relying on H2 as basic fuel. Renewable H2 can be generated using proton exchange membrane (PEM) electrolyzers able to adapt to the varying voltage inputs of intermittent sources. Such PEM electrolyzers operate in acidic environments requiring corrosion-resistant catalysts for the H2 and O2 evolution reactions (HER &...


    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  10. Toxicology and pharmacology of some euthenium compounds: vascular smooth muscle relaxation by nitrosyl derivatives of ruthenium and iridium

    Energy Technology Data Exchange (ETDEWEB)

    Kruszyna, H.; Kruszyna, R.; Hurst, J.; Smith, R.P.


    A series of compounds were synthesized from ruthenium trichloride, and their ip LD50s were determined in mice: pentamminenitrosylruthenium(II) chloride, 8.9; chloronitrobis(2,2'-dipyridyl)ruthenium(II), 55; dichlorobis(2,2'-dipyridyl)ruthenium(II) 63; ruthenium trichloride, 108; and potassium pentachloronitrosylruthenate(II), 127 mg/kg. The two bis-bipyridyl complexes produced death in convulsions within minutes, whereas the remaining compounds resulted in long, debilitating courses with death occuring in 4 to 7 d. When given in massive overdoses, however, the compounds with inorganic ligands also produced rapid convulsive death in mice, and when given iv to anesthetized cats, they produced respiratory arrest. The major toxic effects of all the complexes appeared to be due to the metal and not to its associated ligands. Only complexes having a nitrosyl ligand specifically relaxed vascular smooth muscle. Potassium pentabromoiridate(III) also relaxed rabbit aortic strips that had been contracted by adrenergic argonists, but potassium pentachloroiridate(III) did not. None of the complexes was as active as nitroprusside in relaxing aortic strips or in decreasing arterial blood pressure in cats. No compound tested was as potent as cisplatin in antitumor activity. The pentamminenitrosylruthenium(II) complex also relaxed guinea pig ileum and frog rectus abdominum when these isolated muscles had been contracted by acetylcholine. It appears that these organoruthenium compounds may produce death in central respiratory arrest, as do the inorganic complexes when given iv or ip in massive overdoses. In minimllylethal doses, the complexes with inorganic ligands may affect a variety of contractile tissues, perhaps by a general mechanism involving Ca. These complexes are apt to be generally cytotoxic as well.

  11. Microtektites and Associated Minerals in the Iridium-Rich Layer of Marine Clay From the Central North Pacific Ocean (United States)

    Leung, I. S.


    Our study is based on a sample derived from a deep sea core (GPC3) from the mid-Pacific Ocean floor north of the Hawaiian Islands, provided by Jim Broda, Woods Hole Oceanographic Institution. The 65 Ma K/T boundary layer was identified by measurements of magnetic susceptibility (Doh, 1987) and Ir anomaly (Kyte et al., 1995) which peaked at a down-hole depth of 2055-2056 cm. Our sample of red clay was about 5 cubic cm in size. After wet-sieving for the size fraction greater than 38 microns, we hand-picked grains of interest under a binocular microscope. We found 40 microtektites (glass spherules, mostly devitrified), 12 olive-green aggregates composed of talc/magnetite, and 3 green and blue crystals of silicon carbide (SiC). There are many quartz grains having decorated deformation lamellae or mosaic structures. The olive-green talc/magnetite particles have textures and composition similar to materials found in chondritic meteorites, whereas, SiC crystals are known to occur in carbonaceous chondrites. These particles seem to implicate an affinity to meteorites. Ir-rich deposits world-wide are believed to have settled from dust produced by the Chicxulub Impact, but what object from space created the impact crater is rather uncertain. Our results reported here cannot rule out the possiblilty of impact by comets, because the nature of cometary dust particles are not very well known.

  12. A bis-cyclometalated iridium complex as a benchmark sensitizer for efficient visible-to-UV photon upconversion. (United States)

    Duan, Pengfei; Yanai, Nobuhiro; Kimizuka, Nobuo


    To resolve the biggest problem in visible-to-UV photon upconversion based on sensitized triplet-triplet annihilation-the quenching of upconverted fluorescence by sensitizers-we discovered a superior sensitizer with less UV absorption intensity that enables highly efficient, low-power (0.78 mW cm(-2)) visible-to-UV upconversion.

  13. CCDC 1050374: Experimental Crystal Structure Determination : trichloro-(4'-ferrocenyl-2,2':6',2''-terpyridine)-iridium(iii) acetonitrile solvate

    KAUST Repository

    Davaasuren, Bambar


    An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  14. Iridium- and ruthenium-catalysed synthesis of 2,3-disubstituted indoles from anilines and vicinal diols

    DEFF Research Database (Denmark)

    Tursky, Matyas; Lorentz-Petersen, Linda Luise Reeh; Olsen, L. B.;


    A straightforward and atom-economical method is described for the synthesis of 2,3-disubstituted indoles. Anilines and 1,2-diols are condensed under neat conditions with catalytic amounts of either [Cp*IrCl2](2)/MsOH or RuCl3 center dot xH(2)O/phosphine (phosphine = PPh3 or xantphos). The reaction...

  15. Base-Free Production of H2 by Dehydrogenation of Formic Acid Using An Iridium-bisMETAMORPhos Complex

    NARCIS (Netherlands)

    Oldenhof, S.; de Bruin, B.; Lutz, M.|info:eu-repo/dai/nl/304828971; Siegler, M.A.M.|info:eu-repo/dai/nl/31411744X; Patureau, F.W.; van der Vlugt, J.I.; Reek, J.N.H.


    Hydrogen holds the potential to be one of the major energy carriers for the future. However, a hydrogen-based economy requires technology that allows efficient and safe storage and release of H2. In this light, the reversible storage of dihydrogen in the form of formic acid (HCOOH) provides an

  16. DFT Methods to Study the Reaction Mechanism of Iridium-Catalyzed Hydrogenation of Olefins: Which Functional Should be Chosen? (United States)

    Sun, Yihua; Chen, Hui


    To enable the selection of more accurate computational methods for the future theoretical exploration of the reaction mechanism of Ir-catalyzed olefin hydrogenation, we compared high-level ab initio coupled cluster and DFT calculations with a simplified model of Pfaltz's Ir/P,N-type catalyst for all four previously proposed Ir(I) /Ir(III) and Ir(III) /Ir(V) mechanisms. Through the systematic assessment of the DFT performances, the DFT empirical dispersion correction (DFT-D3) is found to be indispensable for improving the accuracy of relative energies between the Ir(I) /Ir(III) and Ir(III) /Ir(V) mechanisms. After including the DFT-D3 correction, the three best performing density functionals (DFs) are B2-PLYP, BP86, and TPSSh. In these recommended DFs, the computationally more expensive double-hybrid functional B2-PLYP-D3 has a balanced and outstanding performance for calculations of the reaction barriers, reaction energies, and energy gaps between different mechanisms, whereas the less costly BP86-D3 and TPSSh-D3 methods have outstanding, but relatively less uniform performances.

  17. Feasibility Analysis on the Utilization of the Iridium Satellite Communications Network for Resident Space Objects in Low Earth Orbit (United States)


    equatorial speed. Ideally, the GEO satellite remains directly overhead in the absence of perturbing forces. Of course , perturbing forces exist and cause a...respectively. Assuming a mean Earth radius of 6371 km, the Earth- central angles and can be found from trigonometry using the footprint

  18. Efficient Sensitized Z→E Photoisomerization of an Iridium(III)-Azobenzene Complex over a Wide Concentration Range. (United States)

    Moreno, Javier; Grubert, Lutz; Schwarz, Jutta; Bléger, David; Hecht, Stefan


    To improve the sensitized Z→E photoisomerization of azobenzenes, and circumvent the threshold concentration necessary for the bimolecular photoinduced electron transfer reaction to generate the rapidly isomerizing Z-azobenzene radical anion, an Ir(III) complex with a covalently tethered azobenzene fragment was synthesized. Selective irradiation of the (1) MLCT band of the Ir(III) complex induced an efficiently sensitized photoswitching of the dyad over a wide concentration range and even at high dilution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Specific heat study of the iridium double perovskite Sr{sub 2}YIrO{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Corredor, Laura T.; Manna, Kaustuv; Aslan Cansever, Gizem; Gass, Sebastian; Zimmermann, Andreas; Dey, Tushar; Blum, Christian; Maljuk, Andrey; Wurmehl, Sabine; Wolter, Anja; Buechner, Bernd [Leibniz Institute for Solid State and Materials Research Dresden, IFW Dresden (Germany)


    Recently, Mott insulators with a d{sup 4} electronic configuration were predicted to show superexchange-driven quantum phase transitions. Double perovskites R{sub 2}MM{sup '}O{sub 6} with M{sup '3+} ion, yielding a formal oxidation state of Ir{sup 5+} with 5d{sup 4} electronic configuration, may be candidates to verify or discard such transitions and its impact on the magnetic structure. According to the strong spin-orbit coupling J{sub eff} model, a non-magnetic ground state is expected. Such material is realized in Sr{sub 2}YIrO{sub 6}. Nevertheless, it is claimed that a strong non-cubic crystal field together with a ''intermediate-strength'' spin-orbit coupling, would lead to a different ground state configuration and to antiferromagnetic behavior with T{sub N} = 1.3 K. Also, anomalies in the specific heat were associated to this novel magnetism. In this work, we present magnetic and thermodynamic characterization of Sr{sub 2}YIrO{sub 6} single crystals. No long magnetic order was found. The magnetic contribution to the specific heat was calculated, finding a Schottky anomaly due to magnetic impurities. Further analysis suggests non-negligible spin correlations, which nonetheless, are not associated with long range magnetic ordering.

  20. Large Size Color-tunable Electroluminescence from Cationic Iridium Complexes-based Light-emitting Electrochemical Cells (United States)

    Zeng, Qunying; Li, Fushan; Guo, Tailiang; Shan, Guogang; Su, Zhongmin


    Solution-processable light-emitting electrochemical cells (LECs) with simple device architecture have become an attractive candidate for application in next generation lighting and flat-panel displays. Herein, single layer LECs employing two cationic Ir(III) complexes showing highly efficient blue-green and yellow electroluminescence with peak current efficiency of 31.6 cd A‑1 and 40.6 cd A‑1, respectively, have been reported. By using both complexes in the device, color-tunable LECs with a single spectral peak in the wavelength range from 499 to 570 nm were obtained by varying their rations. In addition, the fabrication of efficient LECs was demonstrated based on low cost doctor-blade coating technique, which was compatible with the roll to roll fabrication process for the large size production. In this work, for the first time, 4 inch LEC devices by doctor-blade coating were fabricated, which exhibit the efficiencies of 23.4 cd A‑1 and 25.4 cd A‑1 for the blue-green and yellow emission, respectively. The exciting results indicated that highly efficient LECs with controllable color could be realized and find practical application in large size lighting and displays.