WorldWideScience

Sample records for tetrathiafulvalene

  1. π-Extended Tetrathiafulvalenes

    DEFF Research Database (Denmark)

    Petersen, Johannes Fabritius

    This Ph.D.-thesis focuses on the synthesis and properties of various redox-active ¼-extended tetrathiafulvalenes. One class of molecules are so-called H-cruciform shaped molecules. In these molecules the formation of a central stilbene double bond is elucidated. Here it was found that the formation...... of the stilbene bond originates from preformation of a 1,3-dioxa-2-phospholane, formed by reaction between P(OEt)3 present under the reaction conditions and two aldehydes. Under the reaction conditions this 1,3-dioxa-2-phospholane can then be converted to the stilbene. These mechanistic studies lead...

  2. A Novel Tetrathiafulvalene Building Block

    DEFF Research Database (Denmark)

    Jeppesen, Jan Oskar; Takimiya, Kazuo; Thorup, Niels

    1999-01-01

    Efficient synthesis of a novel tetrathiafulvalene building block. 2,3-bis(2-cyanoethylthio)-6,7-bis(thiocyanato-methyl)tetrathiafulv alene (7) useful for stepwise and asymmetrical bis-function-alization is reported.......Efficient synthesis of a novel tetrathiafulvalene building block. 2,3-bis(2-cyanoethylthio)-6,7-bis(thiocyanato-methyl)tetrathiafulv alene (7) useful for stepwise and asymmetrical bis-function-alization is reported....

  3. Tetrathiafulvalene- (TTF-) Derived Oligopyrrolic Macrocycles

    DEFF Research Database (Denmark)

    Jana, Atanu; Ishida, Masatoshi; Park, Jung Su

    2017-01-01

    After the epochal discovery of the “organic metal”, namely, tetrathiafulvalene (TTF)–7,7,8,8-tetracyano-p-quinodimethane (TCNQ) dyad in 1973, scientists have made efforts to derivatize TTF for constructing various supramolecular architectures to control the charge-transfer processes by adjusting ...

  4. Convergent Synthesis of Rigid Macrocycles Containing One and Two Tetrathiafulvalene Units

    DEFF Research Database (Denmark)

    Simonsen, Klaus B.; Thorup, Niels; Becher, Jan

    1997-01-01

    The synthesis of rigid tetrathiafulvalenophanes containing one or two tetrathiafulvalene units is presented, together with a stepwise convergent synthesis of macrocyclic bis-tetrathiafulvalenes via several open dimeric tetrathiafulvalenes. These systems were investigated by cyclic voltammetry...

  5. Tetrathiafulvalene S-oxide: a Potential Donor Impurity in the Organic Metal TTF-TCNQ

    DEFF Research Database (Denmark)

    Carlsen, Lars; Bechgaard, Klaus; Jacobsen, Claus Schelde

    1979-01-01

    Tetrathiafulvalene S-oxide, which because of its size similarity with tetrathiafulvalene is a potential ‘donor impurity’ in the organic metal TTF–TCNQ, was prepared and characterized spectroscopically. Experiments in which tetrathiafulvalene S-oxide was purposely doped into TTF–TCNQ indicate, how...

  6. A colorimetric tetrathiafulvalene-calix 4 pyrrole anion sensor

    DEFF Research Database (Denmark)

    Nielsen, K. A.

    2012-01-01

    The interaction and colorimetric sensing properties of a tetrathiafulvalene substituted calix[4]pyrrole sensor with anions were investigated using H-1 NMR and absorption spectroscopic techniques. Visual color changes were observed upon addition of different anions (Cl-, Br-, CN-, and AcO-) to a s......The interaction and colorimetric sensing properties of a tetrathiafulvalene substituted calix[4]pyrrole sensor with anions were investigated using H-1 NMR and absorption spectroscopic techniques. Visual color changes were observed upon addition of different anions (Cl-, Br-, CN-, and Ac......O-) to a solution of the sensor. (C) 2012 Elsevier Ltd. All rights reserved....

  7. Urethane tetrathiafulvalene derivatives: synthesis, self-assembly and electrochemical properties

    Directory of Open Access Journals (Sweden)

    Xiang Sun

    2015-11-01

    Full Text Available This paper reports the self-assembly of two new tetrathiafulvalene (TTF derivatives that contain one or two urethane groups. The formation of nanoribbons was evidenced by scanning electron microscopy (SEM and X-ray diffraction (XRD, which showed that the self-assembly ability of T1 was better than that of T2. The results revealed that more urethane groups in a molecule did not necessarily instigate self-assembly. UV–vis and FTIR spectra were measured to explore noncovalent interactions. The driving forces for self-assembly of TTF derivatives were mainly hydrogen bond interactions and π–π stacking interactions. The electronic conductivity of the T1 and T2 films was tested by a four-probe method.

  8. New anthracene-tetrathiafulvalene derivative-encapsulated SWNT nanocomposite and its application for biosensing.

    Science.gov (United States)

    Song, Min; Wang, Xuemei; Liu, Wei; Zuo, Jinglin

    2010-03-01

    In this study, a novel anthracene-tetrathiafulvalene derivative has been synthesized and immobilized on single-walled carbon nanotubes through non-covalent sidewall functionalization. The new anthracene-tetrathiafulvalene (TTF) derivative-encapsulated SWNT nanocomposites were characterized using SEM, TEM, and Raman spectra and were utilized for biomolecular recognition. Our observations demonstrate that the new anthracene-TTF derivative-encapsulated SWNT nanocomposites can readily facilitate the biosensing and sensitive detection of DNA, which could be further explored for promising applications in bioelectronics and biosensors. 2009 Elsevier Inc. All rights reserved.

  9. Self-Assembly of Dimeric Tetrathiafulvalene-Calix 4 pyrrole: Receptor for 1,375-Trinitrobenzene

    DEFF Research Database (Denmark)

    Nielsen, K. A.; Stein, P. C.

    2011-01-01

    The synthesis and binding properties of a tetrathiafulvalene (TTF)-calix[4]pyrrole receptor 2 appended with one 3,5-dinitrobenzoate guest moiety are reported. The preliminary studies revealed that the receptor is self-compiexing into a dimer receptor 2 center dot 2. The self-complexation of the r......The synthesis and binding properties of a tetrathiafulvalene (TTF)-calix[4]pyrrole receptor 2 appended with one 3,5-dinitrobenzoate guest moiety are reported. The preliminary studies revealed that the receptor is self-compiexing into a dimer receptor 2 center dot 2. The self...

  10. Potential model for tetrathiafulvalene based on inelastic neutron scattering and Raman spectra

    NARCIS (Netherlands)

    Burns, G.R.; Favier, F.; Jones, D.J.; Rozière, J.; Kearley, G.J.

    2003-01-01

    Tetrathiafulvalene (TTF) is a key molecule in the family of charge-transfer salts of interest for their novel transport properties. The correspondence between transport property and electron-molecular vibration coupling requires that we understand the phonon density of states for these materials.

  11. A flexible cyclophane: Design, synthesis, and structure of a multibridged tris-tetrathiafulvalene (TTF) macrocycle

    DEFF Research Database (Denmark)

    Takimiya, K.; Thorup, Niels; Becher, J.

    2000-01-01

    The tris-tetrathiafulvalene (TTF) macrocycles 3 with a large end-cavity were effectively synthesized from the readily available tetrakis(cyanoethylthio)TTF by means of a selective deprotection/realkylation sequence followed by an intramolecular coupling reaction. Crystal structure analyses revealed...

  12. Tetraceno[2,1,12,11-opqra]tetracene-extended tetrathiafulvalene - redox-controlled generation of a large PAH core

    DEFF Research Database (Denmark)

    Broman, Søren Lindbæk; Andersen, Cecilie Lindholm; Jousselin-Oba, Tanguy

    2017-01-01

    Two tetraceno[2,1,12,11-opqra]tetracene-extended tetrathia-fulvalenes were prepared and found to undergo reversible conversion into their planar polycyclic aromatic hydrocarbons (PAHs) upon electrochemical oxidation – at potentials probing the best valence bond representations......Two tetraceno[2,1,12,11-opqra]tetracene-extended tetrathia-fulvalenes were prepared and found to undergo reversible conversion into their planar polycyclic aromatic hydrocarbons (PAHs) upon electrochemical oxidation – at potentials probing the best valence bond representations...

  13. A Self-Assembled Electro-Active M8L4 Cage Based on Tetrathiafulvalene Ligands

    Directory of Open Access Journals (Sweden)

    Sébastien Goeb

    2014-01-01

    Full Text Available Two self-assembled redox-active cages are presented. They are obtained by coordination-driven self-assembly of a tetra-pyridile tetrathiafulvalene ligand with cis-M(dppf(OTf2 (M = Pd or Pt; dppf = 1,1′-bis(diphenylphosphinoferrocene; OTf = trifluoromethane-sulfonate complexes. Both species are fully characterized and are constituted of 12 electro-active subunits that can be reversibly oxidized.

  14. Ambient-temperature superconductor symetrical metal-dihalide bis-(ethylenedithio)-tetrathiafulvalene compounds

    Science.gov (United States)

    Williams, Jack M.; Wang, Hsien-Hau; Beno, Mark A.

    1987-01-01

    A new class of organic superconductors having the formula (ET).sub.2 MX.sub.2 wherein ET represents bis(ethylenedithio)-tetrathiafulvalene, M is a metal such as Au, Ag, In, Tl, Rb, Pd and the like and X is a halide. The superconductor (ET).sub.2 AuI.sub.2 exhibits a transition temperature of 5 K. which is high for organic superconductors.

  15. Bis(pyrrolo)tetrathiafulvalene - An Efficient Pi-Donor in Supramolecular Chemistry

    DEFF Research Database (Denmark)

    Lau, Jesper; Nielsen, Mogens Brøndsted; Thorup, Niels

    1999-01-01

    The synthesis of three novel macrocycles 3-5 based on the two electron donors bis(2,5-dimethyl- pyrrolo)[3,4-d]tetrathiafulvalene (1) and 1,4-hydroquinone is presented. Their abilities to include the electron acceptor paraquat (6) have been investigated by UV/Vis and sup 1 H NMR spectroscopy and ......, the preferred position of the cyclic acceptor 7 in the catenanes around either the pyrrolo-annelated TTF or around the hydroquinone donor relies on a fine balance between all the individual noncovalent forces acting in cooperation....

  16. Mono- and bis(pyrrolo)tetrathiafulvalene derivatives tethered to C60

    DEFF Research Database (Denmark)

    Vico Solano, Marta; Della Pia, Eduardo Antonio; Jevric, Martyn

    2014-01-01

    electronic communication between the MPTTF/BPTTF units and the C-60 moieties. In addition, femtosecond and nanosecond transient absorption spectroscopy revealed, rather surprisingly, that no charge transfer from the MPTTF/BPTTF units to the C-60 moieties takes place on excitation of the fullerene moiety......A series of mono- (MPTTF) and bis(pyrrolo) tetrathiafulvalene (BPTTF) derivatives tethered to one or two C-60 moieties was synthesized and characterized. The synthetic strategy for these dumbbell-shaped compounds was based on a 1,3-dipolar cycloaddition reaction between aldehyde...

  17. Chiroptical properties of 1,3-diphenylallene-anchored tetrathiafulvalene and its polymer synthesis

    Directory of Open Access Journals (Sweden)

    Masashi Hasegawa

    2015-06-01

    Full Text Available A novel tetrathiafulvalene dimer, bridged by a chiral 1,3-diphenylallene framework, has been prepared as an optically active compound having strong chiroptical properties. Although a chiral allene bearing strong electron-donating group(s often undergoes slow photoracemization even in daylight, the present allene is totally configurationally stable under ordinary conditions. Each isomer possesses pronounced chiroptical properties in its ECD spectra reflecting the chiral allene framework. Moreover, the elongation of the chiral main chain was also carried out by direct C–H activation of the TTF unit, and the chiroptical properties of the resulting polymer were also investigated.

  18. Ion-Regulated Allosteric Binding of Fullerenes (C-60 and C-70) by Tetrathiafulvalene-Calix[4]pyrroles

    DEFF Research Database (Denmark)

    Davis, C. M.; Lim, J. M.; Larsen, K. R.

    2014-01-01

    The effect of ionic species on the binding of fullerenes (C-60 and C-70) by tetrathiafulvalene-calix[4]pyrrole (TTF-C4P) receptors and the nature of the resulting supramolecular complexes (TTF-C4P + fullerene + halide anion + tetraalkylammonium cation) was studied in the solid state through single...

  19. Electrochemical control of the single molecule conductance of a conjugated bis(pyrrolo)tetrathiafulvalene based molecular switch

    DEFF Research Database (Denmark)

    O'Driscoll, Luke J.; Hamill, Joseph M.; Grace, Iain

    2017-01-01

    (pyrrolo)tetrathiafulvalene (BPTTF) has been designed, synthesised and investigated using scanning tunnelling microscopy break junction (STM-BJ) studies and quantum transport calculations. Oxidising the BPTTF unit increases its conjugation, which was anticipated to increase the molecular conductance of 1. By changing the redox...

  20. Interactions between tetrathiafulvalene units in dimeric structures – the influence of cyclic cores

    Directory of Open Access Journals (Sweden)

    Huixin Jiang

    2015-06-01

    Full Text Available A selection of cyclic and acyclic acetylenic scaffolds bearing two tetrathiafulvalene (TTF units was prepared by different metal-catalyzed coupling reactions. The bridge separating the two TTF units was systematically changed from linearly conjugated ethyne, butadiyne and tetraethynylethene (trans-substituted units to a cross-conjugated tetraethynylethene unit, placed in either acyclic or cyclic arrangements. The cyclic structures correspond to so-called radiaannulenes having both endo- and exocyclic double bonds. Interactions between two redox-active TTF units in these molecules were investigated by cyclic voltammetry, UV–vis–NIR and EPR absorption spectroscopical methods of the electrochemically generated oxidized species. The electron-accepting properties of the acetylenic cores were also investigated electrochemically.

  1. Molecular conductors from bis(ethylenedithio)tetrathiafulvalene with tris(oxalato)rhodate.

    Science.gov (United States)

    Martin, Lee; Morritt, Alexander L; Lopez, Jordan R; Nakazawa, Yasuhiro; Akutsu, Hiroki; Imajo, Shusaku; Ihara, Yoshihiko; Zhang, Bin; Zhang, Yan; Guo, Yanjun

    2017-07-25

    This article reports a family of new radical-cation salts of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with tris(oxalato)rhodate: three salts with the formula β''-(BEDT-TTF)4[(cation)Rh(C2O4)3]·solvent (solvent = fluorobenzene, chlorobenzene, or bromobenzene) and one with the formula pseudo-κ-(BEDT-TTF)4[(NH4)Rh(C2O4)3]·benzonitrile. We report here the syntheses, crystal structures, electrical properties and Raman spectroscopy of these new molecular conductors. The bromobenzene salt shows a decrease in resistivity below 2.5 K indicative of a superconducting transition and a Shubnikov-de Haas oscillation with a frequency of 232 T and effective mass m* of 1.27me.

  2. Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

    Directory of Open Access Journals (Sweden)

    Awatef Ayadi

    2015-08-01

    Full Text Available The synthesis and full characterization of two tetrathiafulvalene-appended azine ligands, namely 2-([2,2’-bi(1,3-dithiolylidene]-4-yl-6-((2,4-dinitrophenylhydrazonomethylpyridine (L1 and 5-([2,2’-bi(1,3-dithiolylidene]-4-yl-2-((2,4-dinitrophenylhydrazonomethylpyridine (L2 are described. The crystal structure of ligand L1 indicates that the ligand is completely planar with the presence of a strong intramolecular N3–H3···O1 hydrogen bonding. Titration experiments with inorganic anions showed that both ligands are suitable candidates for the sensing of fluoride anions. Ligand L2 was reacted with a Re(I cation to yield the corresponding rhenium tricarbonyl complex 3. In the crystal structure of the newly prepared electroactive rhenium complex the TTF is neutral and the rhenium cation is hexacoordinated. The electrochemical behavior of the three compounds indicates that they are promising for the construction of crystalline radical cation salts.

  3. Donor–acceptor type co-crystals of arylthio-substituted tetrathiafulvalenes and fullerenes

    Directory of Open Access Journals (Sweden)

    Xiaofeng Lu

    2015-06-01

    Full Text Available A series of donor–acceptor type co-crystals of fullerene (as the acceptor and arylthio-substituted tetrathiafulvalene derivatives (Ar-S-TTF, as the donor were prepared and their structural features were thoroughly investigated. The formation of co-crystals relies on the flexibility of Ar-S-TTF and the size matches between Ar-S-TTF and fullerene. Regarding their compositions, the studied co-crystals can be divided into two types, where types I and II have donor:acceptor ratios of 1:1 and 1:2, respectively. Multiple intermolecular interactions are observed between the donor and acceptor, which act to stabilize the structures of the resulting co-crystals. In the type I co-crystals, the fullerene molecule is surrounded by four Ar-S-TTF molecules, that is, two Ar-S-TTF molecules form a sandwich structure with one fullerene molecule and the other two Ar-S-TTF molecules interact with the fullerene molecule along their lateral axes. In the type II co-crystals, one fullerene molecule has the donor–acceptor mode similar to that in type I, whereas the other fullerene molecule is substantially surrounded by the aryl groups on Ar-S-TTF molecules and the solvent molecules.

  4. Dynamic self-assembly of charge-transfer nanofibers of tetrathiafulvalene derivatives with F4TCNQ.

    Science.gov (United States)

    Jain, Ankit; Rao, K Venkata; Mogera, Umesha; Sagade, Abhay A; George, Subi J

    2011-10-24

    One-dimensional charge-transfer nanostructures were constructed by the supramolecular coassembly of amphiphilic (Amph-TTF) and hydrophobic (TDD-TTF) tetrathiafulvalene (TTF) donor derivatives with the acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)TCNQ), in appropriate solvent composition mixtures. Microscopic analyses show that TDD-TTF retains its self-assembled fibrillar morphology even in the charge-transfer state, whereas Amph-TTF undergoes a spherical to nanorod transition upon coassembly. Time-dependent optical spectroscopy studies have shown a spontaneous change in molecular organization in TDD-TTF-based donor-acceptor costacks, which suggests a dynamic behavior, in contrast to the kinetically stable amphiphilic TTF assemblies. We have also tried to get an insight into the observed time-dependent change in molecular packing of these nanostructures through spectroscopic analyses by commenting on whether the TTF-TCNQ pair is cofacially arranged or present in the classical herringbone (orthogonal) fashion. Furthermore, our two-probe electrical measurements showed that these charge-transfer fibers are conducting. A supramolecular approach that yields 1D charge-transfer nanostructures of donor and acceptor molecules will be an alternative to existing crystalline substances with high conductivity and hence can be a viable tool for nanoelectronics. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Scanning electron microscope technique for measuring electrical conductivity: application to tetrathiafulvalene--tetracyanoquinodimethane

    Energy Technology Data Exchange (ETDEWEB)

    Long, James Peter [Univ. of Illinois, Urbana-Champaign, IL (United States)

    1977-01-01

    A new technique for measuring the electrical conductivity of small samples and its application to the organic conductor tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) is reported. A movable current source provided by the electron beam of a scanning electron microscope is used to map out the potential distribution on crystal faces containing the a-b crystallographic axes. Silver paint contacts are used to return the beam current to ground and measure voltage changes as the beam position is moved. The results of the new technique are confirmed and complemented by the conventional movable contact method and the extension of both methods to low temperature is discussed. The potential distributions for our samples reveal frequently occurring irregularities in current flow which are attributable to sample imperfections and inhomogeneities in the silver paint contacts. Methods are presented whereby the commonly reported conductivities sigmaa and sigmab can be determined despite the presence of certain current flow irrgularities; room temperature values are found to be: sigmab = 490 ± 80 (Ωcm)-1 and sigmaa = 1.21 ± 0.15 (Ωcm)-1. The relationship of sigmaa/ and sigmab to the elements of the correctly expressed conductivity tensor for TTF-TCNQ is clarified. The influence of contact inhomogeneities on four-probe measurements of the temperature dependence of the b-axis conductivity as determined with an electrolytic tank model are also presented. It is found that there is a large probability of slightly underestimating conductivity, but that it is possible in a small number of cases to greatly overestimate conductivity.

  6. Axially assembled photosynthetic reaction center mimics composed of tetrathiafulvalene, aluminum(iii) porphyrin and fullerene entities

    Science.gov (United States)

    Poddutoori, Prashanth K.; Lim, Gary N.; Sandanayaka, Atula S. D.; Karr, Paul A.; Ito, Osamu; D'Souza, Francis; Pilkington, Melanie; van der Est, Art

    2015-07-01

    The distance dependence of sequential electron transfer has been studied in six, vertical, linear supramolecular triads, (TTF-Phn-py --> AlPor-Phm-C60, n = 0, 1 and m = 1, 2, 3), constructed using tetrathiafulvalene (TTF), aluminum(iii) porphyrin (AlPor) and fullerene (C60) entities. The C60 and TTF units are bound to the Al center on opposite faces of the porphyrin; the C60 through a covalent axial bond using a benzoate spacer, and the TTF through a coordination bond via an appended pyridine. Time-resolved optical and EPR spectroscopic methods and computational studies are used to demonstrate that excitation of the porphyrin leads to step-wise, sequential electron transfer (ET) between TTF and C60, and to study the electron transfer rates and exchange coupling between the components of the triads as a function of the bridge lengths. Femtosecond transient absorption studies show that the rates of charge separation, kCS are in the range of 109-1011 s-1, depending on the length of the bridges. The lifetimes of the charge-separated state TTF&z.rad;+-C&z.rad;-60 obtained from transient absorbance experiments and the singlet lifetimes of the radical pairs obtained by time-resolved EPR are in good agreement with each other and range from 60-130 ns in the triads. The time-resolved EPR data also show that population of the triplet sublevels of the charge-separated state in the presence of a magnetic field leads to much longer lifetimes of >1 μs. The data show that a modest stabilization of the charge separation lifetime occurs in the triads. The attenuation factor β = 0.36 Å-1 obtained from the exchange coupling values between TTF&z.rad;+ and C&z.rad;-60 is consistent with values reported in the literature for oligophenylene bridged TTF-C60 conjugates. The singlet charge recombination lifetime shows a much weaker dependence on the distance between the donor and acceptor, suggesting that a simple superexchange model is not sufficient to describe the back reaction

  7. Timeresolved investigation of atomic order in tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) monocrystals after excitation with ultrashort light pulses; Zeitaufgeloeste Untersuchung atomarer Ordnung in Tetrathiafulvalen-Tetracyanochinodimethan (TTF-TCNQ)-Einkristallen nach Anregung mit ultrakurzen Lichtpulsen

    Energy Technology Data Exchange (ETDEWEB)

    Sager, Christian

    2011-02-15

    This thesis describes time-resolved investigations of the atomic structure of one-dimensional organic molecular crystals after laser excitation of the photo-induced phase transition. There is a neutral to ionic phase transition in tetrathiafulvalene-chloranil-crystals (TTF-CA-crystals). At this phase transition a Peierls distortion occurs. A new model is introduced, that can explain the photo-induced phase transition in TTF-CY-crystals. This model is called charge density wave model of photo induced structural phase transition. There is a structural phase transition in tetrathiafulvalene-tetracyanochinodimethane-crystals (TTF-TCNQ-crystals). At this phase transition the one-dimensional metal TTF-TCNQ is transformed to an insulator. The phase transition is driven by the Peierls distortion. The charge density wave model is appropriate for description of the processes in TTF-TCNQ-crystals after laser excitation. The results of time-resolved measurements of the structure of TTF-TCNQ-crystals after excitation of the photo-induced phase transition can be anticipated with the charge density wave model. In the basis of these anticipated results, a time-resolved measurement for investigation of the atomic structure of TTF-TCNQ after excitation of the photo-induced phase transition is proposed. The time-resolved measurement should be performed at a beamline of a third generation synchrotron by the optical pump X-ray probe technique. The time-resolved measurement is prepared by an optical characterization and by static X-ray diffraction measurements. The results of the optical characterization and the static X-ray diffraction measurements are presented and analyzed. (orig.)

  8. Selective landing of semiconducting single-wall carbon nanotubes onto tetrathiafulvalene moiety self-assembled on ITO substrate

    Directory of Open Access Journals (Sweden)

    Jin-Sun Kim

    2010-03-01

    Full Text Available Semiconducting single-wall carbon nanotubes (SWCNTs were selecively interacted with tetrathiafulvalene (TTF moiety self-assembled on indium tin oxide (ITO substrate by charge-transfer interaction. The charge-transfer phenomena between two molecules were elucidated by cyclic voltammetry (CV and Raman spectroscopy. CV measurement of TTF-modified ITO substrate as a working electrode presented the difference between heat-treated system and untreated one. The two redox potentials, which are typically related to redox behavior of TTF, were shown in the unheated system during both oxidation and reduction cycles, while the two oxidation peaks were disappeared in the heated system. Raman spectra indicated that the intensities of RBM originated from metallic SWCNTs were much reduced in the heat-treated system, while there were little change in the unheated one. These results revealed that only semiconducting SWNTs were selectively adsorbed on the TTF moiety self-assembled on ITO when the system with heat treatment.

  9. New Unsymmetrically Benzene-Fused Bis (Tetrathiafulvalene: Synthesis, Characterization, Electrochemical Properties and Electrical Conductivity of Their Materials

    Directory of Open Access Journals (Sweden)

    Tahar Abbaz

    2014-03-01

    Full Text Available The synthesis of new unsymmetrically benzene-fused bis (tetrathiafulvalene has been carried out by a cross-coupling reaction of the respective 4,5-dialkyl-1,3-dithiole-2-selenone 6–9 with 2-(4-(p-nitrophenyl-1,3-dithiole-2-ylidene-1,3,5,7-tetrathia-s-indacene-6-one 5 prepared by olefination of 4-(p-nitrophenyl-1,3-dithiole-2-selenone 3 and 1,3,5,7-tetrathia-s-indacene-2,6-dione 4. The conversion of the nitro moiety 10a–d to amino 11a–d then dibenzylamine 12a–d groups respectively used reduction and alkylation methods. The electron donor ability of these new compounds has been measured by cyclic voltammetry (CV technique. Charge transfer complexes with tetracyanoquino-dimethane (TCNQ were prepared by chemical redox reactions. The complexes have been proven to give conducting materials.

  10. Modified Laccase-Gold Nanoparticles-Tetrathiafulvalene-SPCEs Based Biosensor to Determine W(VI in Water

    Directory of Open Access Journals (Sweden)

    Ana Lorena Alvarado-Gámez

    2017-04-01

    Full Text Available It was developed an amperometric biosensor to determine tungsten in water, based on the inhibition of laccase enzyme, by tungsten ions using pyrocathecol as a substrate. The enzyme was immobilized with a proper mixture containing, bovine serum albumin, and glutaraldehyde, for a cross-linking process over screen-printed carbon electrodes, previously modified with tetrathiafulvalen and gold nanoparticles. Optimized experimental conditions are: pyrocatechol in cell 0.040 mM in a phosphate buffer pH 6.5 and applied potential +350 mV. The repeatability and reproducibility, in terms of relative standard deviation values, of de developed biosensor were 3.3 % (n=3, and 2.2 % (n = 5 respectively, and detection limit was 1.8 × 10-7 mol L-1. Additionally it was determined the kinetics of the systems by means of Michaelis-Menten Km apparent constants, calculated using Lineweaver-Burk plots, with and without tungsten. Kinetic study resembles to be competitive inhibition. A recovery study was performed with spiked blanks with a tungsten certified reference standard, traceable to NIST, giving as a result 102.3 ± 6.7 %; tap water samples analyzed presented a mean concentration of 1.75 µM, and recovery of the tungsten certified reference standard on the tap water samples gave 98.8 ± 3.1 %.

  11. Mono- and bis(pyrrolo)tetrathiafulvalene derivatives tethered to C60: synthesis, photophysical studies, and self-assembled monolayers.

    Science.gov (United States)

    Solano, Marta Vico; Della Pia, Eduardo Antonio; Jevric, Martyn; Schubert, Christina; Wang, Xintai; van der Pol, Cornelia; Kadziola, Anders; Nørgaard, Kasper; Guldi, Dirk M; Nielsen, Mogens Brøndsted; Jeppesen, Jan O

    2014-08-04

    A series of mono- (MPTTF) and bis(pyrrolo)tetrathiafulvalene (BPTTF) derivatives tethered to one or two C60 moieties was synthesized and characterized. The synthetic strategy for these dumbbell-shaped compounds was based on a 1,3-dipolar cycloaddition reaction between aldehyde-functionalized MPTTF/BPTTF derivatives, two different tailor-made amino acids, and C60. Electronic communication between the MPTTF/BPTTF units and the C60 moieties was studied by a variety of techniques including cyclic voltammetry and absorption spectroscopy. These solution-based studies indicated no observable electronic communication between the MPTTF/BPTTF units and the C60 moieties. In addition, femtosecond and nanosecond transient absorption spectroscopy revealed, rather surprisingly, that no charge transfer from the MPTTF/BPTTF units to the C60 moieties takes place on excitation of the fullerene moiety. Finally, it was shown that the MPTTF-C60 and C60-BPTTF-C60 dyad and triad molecules formed self-assembled monolayers on a Au(111) surface by anchoring to C60. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Tetrathiafulvalene-Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open-Shell Characteristics on Linear and Nonlinear Optical Properties.

    Science.gov (United States)

    Souto, Manuel; Calbo, Joaquín; Ratera, Imma; Ortí, Enrique; Veciana, Jaume

    2017-08-16

    Three conjugated donor-π-acceptor radical systems (1 a-1 c) were prepared by bridging a tetrathiafulvalene (TTF) electron-donor unit to a polychlorotriphenylmethyl (PTM) electron-acceptor radical through vinylene units of different lengths. The dependence of the intramolecular charge transfer on the length of the conjugated bridge has been analyzed by different electrochemical and spectroscopic techniques. Linear optical properties and the second-order nonlinear optical (NLO) response of these derivatives have been computed by comparing systems 1 a-1 c with the non-radical analogues (2 a-2 c). Interestingly, an enhanced NLO response is predicted for dyads 1 a-1 c with PTM in the radical form and for compounds with longer vinylene bridges. Calculations confirm the active role the bridge plays for electronic communication between the donor TTF and the acceptor PTM units. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Bipyridinium Polymers That Dock Tetrathiafulvalene Guests in Water Driven by Donor-Acceptor and Ion Pair Interactions.

    Science.gov (United States)

    Zhang, Yun-Chang; Qin, Ying; Wang, Hui; Zhang, Dan-Wei; Yang, Guanyu; Li, Zhan-Ting

    2016-04-05

    Two water-soluble para-xylylene-connected 4,4'-bipyridinium (BIPY(2+) ) polymers have been prepared. UV-Vis absorption, (1) H NMR spectroscopy, and cyclic voltammetry experiments support that in water the BIPY(2+) units in the polymers form stable 1:1 charge-transfer complexes with tetrathiafulvalene (TTF) guests that bear two or four carboxylate groups. These charge-transfer complexes are stabilized by the donor-acceptor interaction between electron-rich TTF and electron-deficient BIPY(2+) units and electrostatic attraction between the dicationic BIPY(2+) units and the anionic carboxylate groups attached to the TTF core. On the basis of UV-Vis experiments, a lower limit to the apparent association constant of the TTF⋅BIPY(2+) complexes of the mixtures, 1.8×10(6)  m(-1) , has been estimated in water. Control experiments reveal substantially reduced binding ability of the neutral TTF di- and tetracarboxylic acids to the BIPY(2+) molecules and polymers. Moreover, the stability of the charge-transfer complexes formed by the BIPY(2+) units of the polymers are considerably higher than that of the complexes formed between two monomeric BIPY(2+) controls and the dicarboxylate-TTF donor; this has been attributed to the mutually strengthened electron-deficient nature of the BIPY(2+) units of the polymers due to the electron-withdrawing effect of the BIPY(2+) units. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Ion-regulated allosteric binding of fullerenes (C60 and C70) by tetrathiafulvalene-calix[4]pyrroles.

    Science.gov (United States)

    Davis, Christina M; Lim, Jong Min; Larsen, Karina R; Kim, Dong Sub; Sung, Young Mo; Lyons, Dani M; Lynch, Vincent M; Nielsen, Kent A; Jeppesen, Jan O; Kim, Dongho; Park, Jung Su; Sessler, Jonathan L

    2014-07-23

    The effect of ionic species on the binding of fullerenes (C60 and C70) by tetrathiafulvalene-calix[4]pyrrole (TTF-C4P) receptors and the nature of the resulting supramolecular complexes (TTF-C4P + fullerene + halide anion + tetraalkylammonium cation) was studied in the solid state through single crystal X-ray diffraction methods and in dichloromethane solution by means of continuous variation plots and UV-vis spectroscopic titrations. These analyses revealed a 1:1 stoichiometry between the anion-bound TTF-C4Ps and the complexed fullerenes. The latter guests are bound within the bowl-like cup of the C4P in a ball-and-socket binding mode. The interactions between the TTF-C4P receptors and the fullerene guests are highly influenced by both the nature of halide anions and their counter tetraalkylammonium cations. Three halides (F(-), Cl(-), and Br(-)) were studied. All three potentiate the binding of the two test fullerenes by inducing a conformational change from the 1,3-alternate to the cone conformer of the TTF-C4Ps, thus acting as positive heterotropic allosteric effectors. For a particular halide anion, the choice of tetraalkylammonium salts serves to modulate the strength of the TTF-C4P-fullerene host-guest binding interactions and, in conjunction with variations in the halide anion, can be exploited to alter the inherent selectivity of the host for a given fullerene. Differences in binding are reflected in the excited state optical properties. Overall, the present four-component system provides an illustration of how host-guest binding events involving appropriately designed artificial receptors can be fine-tuned via the addition of simple ionic species as allosteric modulators.

  15. A new type of charge-transfer salts based on tetrathiafulvalene-tetracarboxylate coordination polymers and methyl viologen.

    Science.gov (United States)

    Huang, Yu-De; Huo, Peng; Shao, Ming-Yan; Yin, Jing-Xue; Shen, Wei-Chun; Zhu, Qin-Yu; Dai, Jie

    2014-04-07

    Although charge-transfer compounds based on tetrathiafulvalene (TTF) derivatives have been intensively studied, {[cation](n+)·[TTFs](n-)} ion pair charge-transfer (IPCT) salts have not been reported. The aim of this research is to introduce functional organic cations, such as photoactive methyl viologen (MV(2+)), into the negatively charged TTF-metal coordination framework to obtain this new type of IPCT complex. X-ray structural analysis of the four compounds (MV)2[Li4(L)2(H2O)6] (1), {(MV)(L)[Na2(H2O)8]·4H2O}n (2), {(MV)[Mn(L)(H2O)2]·2H2O}n (3), and {(MV)[Mn(L)(H2O)2]}n (4), reveals that the electron donor (D) TTF moiety and the electron acceptor (A) MV(2+) form a regular mixed-stack arrangement in alternating DADA fashion. The TTF moiety and the MV(2+) cation are essentially parallel stacked to form the column structures. The strong electrostatic interaction is a main force to shorten the distance between the cation and anion planes. Optical diffuse-reflection spectra indicate that charge transfer occurs in these complexes. The ESR and magnetic measurements confirm that there is strong charge-transfer-induced partial electron transfer. Compounds 2, 3, and 4 show an effective and repeatable photocurrent response. The current intensities of 3 and 4 are higher than that of 2, which reflects that the coordination center of the Mn(II) ion has a great effect on the increasing photocurrent response.

  16. Tuning crystal polymorphs of a Π-extended tetrathiafulvalene-based cruciform molecule towards high-performance organic field-effect transistors

    DEFF Research Database (Denmark)

    Feng, Linlin; Dong, Huanli; Li, Qingyuan

    2017-01-01

    packing arrangements in solid state) towards efficient charge transport and high performance devices. Here, the choice of solvent had a marked effect on controlling the growth of α-phase ribbon and β-phase platelet during crystallization for an indenofluorene (IF) π-extended tetrathiafulvalene (TTF......It is a common phenomenon for organic semiconductors to crystallize in two or more polymorphs, leading to various molecular packings and different charge transport properties. Therefore, it is a crucial issue of tuning molecular crystal polymorphs (i.e., adjusting the same molecule with different......)-based cruciform molecule, named as IF-TTF. The charge carrier mobility of the α-phase IF-TTF crystals was more than one order of magnitude higher than that of β-phase crystals, suggesting the importance of reasonably tuning molecular packing in solid state for the improvement of charge transport in organic...

  17. Vesicle self-assembly by tetrathiafulvalene derivatives in both polar and nonpolar solvents and pseudo-rotaxane mediated vesicle-to-microtube transformation.

    Science.gov (United States)

    Zhang, Kang-Da; Wang, Gui-Tao; Zhao, Xin; Jiang, Xi-Kui; Li, Zhan-Ting

    2010-05-18

    This paper reports the self-assemblies of vesicles from two tetrathiafulvalene (TTF) derivatives (T1 and T2), that bear four or two amphiphilic side chains, in both polar and nonpolar solvents. The formation of vesicles is evidenced by scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), and dynamic light scattering (DLS) experiments, while the microstructural aspects of the vesicles are investigated by UV-vis, (1)H NMR, and high resolution TEM, which support a monolayer model for the vesicles. It is revealed that the formation of vesicles is driven by the combination of multiple noncovalent interactions, including pi-pi stacking, hydrogen-bonding, van der Waals force, and S...S interactions. It is also found that, in the presence of electron-deficient cyclobis(paraquat-p-phenylene) tetracation cyclophane, vesicles of T2 can transform into microtubes as a result of the formation of the pseudo[2]rotaxane between the TTF unit of T2 and the cyclophane. This process can be reversed by introducing pristine TTF into the solution of microtubes, due to release of T2 from the pseudo[2]rotaxane through the formation of a more stable complex between pristine TTF and tetracation cyclophane.

  18. Two Closely Related Organic Charge-Transfer Complexes Based on Tetrathiafulvalene and 9H-fluorenone Derivatives. Competition between Hydrogen Bonding and Stacking Interactions

    Directory of Open Access Journals (Sweden)

    Amparo Salmerón-Valverde

    2015-06-01

    Full Text Available Two 1:1 charge-transfer organic complexes were formed using tetrathiafulvalene as a donor and a 9H-fluorenone derivative as acceptor: 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid (complex 1 or 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid methyl ester (complex 2. Both systems crystallize with alternated donor and acceptor stacks. However, the crystal structure of 1 is influenced by classical hydrogen bonds involving carboxylic acid groups, which force to arrange acceptors as centrosymmetric dimers in the crystal, via R2 2(8 ring motifs, while such a restriction is no longer present in the case of 2, affording thus a different crystal structure. This main difference is reflected in stacking interactions, and, in turn, in the degree of charge transfer observed in the complexes. The degree of charge transfer, estimated using Raman spectroscopy, is δ1 = 0.07 for 1 and δ2 = 0.14 for 2. It thus seems that, at least for the studied complexes, hydrogen bonding is an unfavorable factor for charge transfer.

  19. Single-molecule conductance of a chemically modified, π-extended tetrathiafulvalene and its charge-transfer complex with F4TCNQ

    Directory of Open Access Journals (Sweden)

    Raúl García

    2015-06-01

    Full Text Available We describe the synthesis and single-molecule electrical transport properties of a molecular wire containing a π-extended tetrathiafulvalene (exTTF group and its charge-transfer complex with F4TCNQ. We form single-molecule junctions using the in situ break junction technique using a homebuilt scanning tunneling microscope with a range of conductance between 10 G0 down to 10−7 G0. Within this range we do not observe a clear conductance signature of the neutral parent molecule, suggesting either that its conductance is too low or that it does not form a stable junction. Conversely, we do find a clear conductance signature in the experiments carried out on the charge-transfer complex. Due to the fact we expected this species to have a higher conductance than the neutral molecule, we believe this supports the idea that the conductance of the neutral molecule is very low, below our measurement sensitivity. This idea is further supported by theoretical calculations. To the best of our knowledge, these are the first reported single-molecule conductance measurements on a molecular charge-transfer species.

  20. Coupling of metal-based light-harvesting antennas and electron-donor subunits: Trinuclear Ruthenium(II) complexes containing tetrathiafulvalene-substituted polypyridine ligands

    DEFF Research Database (Denmark)

    Campagna, Sebastiano; Serroni, Scolastica; Puntoriero, Fausto

    2002-01-01

    as light-harvesting antennas and the tetrathiafulvalene electron donors can induce charge separation. The absorption spectra, redox behavior, and luminescence properties (both at room temperature in acetonitrile and at 77 K in a rigid matrix of butyronitrile) of the trinuclear metal complexes have been......(mu-2,3-dpp)}(2)Ru(bpy-TTF1)](PF6)(6) (9; bpy=2,2'-bipyridine; 2,3-dpp = 2,3-bis(2'-pyridyl)pyrazine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy-TTF2)](PF6)(6) (10). These compounds can be viewed as coupled antennas and charge-separation systems, in which the multichromophoric trinuclear metal subunits act......+) (4,4'-Mebpy = 4,4'-dimethyl-2,2'-bipyridine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy)](6+). The absorption spectra and redox behavior of all the new metal compounds can be interpreted by a multicomponent approach, in which specific absorption features and redox processes can be assigned to specific...

  1. Crystal structure and electrical conductivity of {alpha}'''-[BEDT-TTF]{sub 12}[Cu{sub 2}Br{sub 4}]{sub 3} (BEDT-TTF=bis(ethylenedithio)tetrathiafulvalene)

    Energy Technology Data Exchange (ETDEWEB)

    Kubo, Kazuya, E-mail: kkubo@m.tains.tohoku.ac.j [Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-Ku, Sendai, Miyagi 980-8578 (Japan); Miyasaka, Hitoshi; Yamashita, Masahiro [Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aramaki-Aza-Aoba, Aoba-Ku, Sendai, Miyagi 980-8578 (Japan)

    2010-06-01

    A new non-integer valence salt based on bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with a dianionic dinuclear cupper(I) complex, {alpha}'''-[BEDT-TTF]{sub 12}(Cu{sup I}{sub 2}Br{sub 4}){sub 3}, was selectively synthesized by a diffusion of BEDT-TTF in tetrahydrofurane (THF) and a mixture of Cu{sup II}X{sub 2} (X=Br or Cl) in methanol. An alternating stacking arrangement of the BEDT-TTF layers and inorganic layers of the Cu{sup I}{sub 2}Br{sub 4}{sup 2-} anions is formed, where the BEDT-TTF layer involves six crystallographically independent molecules. Overlap integral calculation among BEDT-TTF donors in the salt suggests the existence of two-dimensional interactions among the donors. The compound exhibits semiconducting behavior in the wide range of temperature of room temperature to 2 K ({rho}{sub r.t.}=0.3 {Omega} cm, E{sub a}=0.08 eV in a crystal) without structural phase transition at ambient pressure.

  2. Mass Spectra of Tetraselenafulvalenes, Diselenadithiafulvalenes and Tetrathiafulvalenes

    DEFF Research Database (Denmark)

    Andersen, Jan Rud; Egsgaard, Helge; Larsen, Elfinn

    1978-01-01

    The mass spectra of 13 heterofulvalenes are reported. The spectra show great similarities within the selenium and within the sulphur series. The main difference between the selenium and the sulphur compounds results from the more facile loss of selenium compared with sulphur, and from the first...

  3. Synthesis and recognition properties of higher order tetrathiafulvalene (TTF) calix n pyrroles (n=4-6)

    DEFF Research Database (Denmark)

    Park, J. S.; Bejger, C.; Larsen, K. R.

    2012-01-01

    Two new benzoTTF-annulated calix[n]pyrroles (n = 5 and 6) were synthesized via a one-step acid catalyzed condensation reaction and fully characterized via single crystallographic analyses. As compared to the known tetra-TTF annulated calix[4]pyrrole, which is also produced under the conditions...... effective for the recognition of TNB and TNT. These findings are rationalized in terms of the number of electron rich TTF subunits and NH hydrogen bond donor groups within the series, as well as an ability to adopt conformations suitable for substrate recognition, and are supported by solid state structural...

  4. Ionic manipulation of charge-transfer and photodynamics of [60]fullerene confined in pyrrolo-tetrathiafulvalene cage

    DEFF Research Database (Denmark)

    Bähring, Steffen; Larsen, Karina R; Supur, Mustafa

    2017-01-01

    A cage molecule incorporating three electron donating monopyrrolotetrathiafulvalene units was synthesised to host electron accepting [60]fullerenes. Formation of a strong 1 : 1 donor-acceptor (D-A) complex C60⊂1 was confirmed by solid state X-ray analysis as well as (1)H NMR and absorption...... spectroscopic analyses of the arising charge-transfer (CT) band (λ = 735 nm, ε ≈ 840 M(-1) cm(-1)). Inserting Li(+) inside the [60]fullerene increased the binding 28-fold (Ka = 3.7 × 10(6) M(-1)) and a large bathochromic shift of the CT band to the near infrared (NIR) region (λ = 1104 nm, ε ≈ 4800 M(-1) cm(-1...

  5. Mechanochemical Synthesis of Two Polymorphs of the Tetrathiafulvalene-Chloranil Charge Transfer Salt: An Experiment for Organic Chemistry

    Science.gov (United States)

    Wixtrom, Alex; Buhler, Jessica; Abdel-Fattah, Tarek

    2014-01-01

    Mechanochemical syntheses avoid or considerably reduce the use of reaction solvents, thus providing green chemistry synthetic alternatives that are both environmentally friendly and economically advantageous. The increased solid-state reactivity generated by mechanical energy imparted to the reactants by grinding or milling can offer alternative…

  6. Robust Inclusion Complexes of Crown Ether Fused Tetrathiafulvalenes with Li+@C-60 to Afford Efficient Photodriven Charge Separation

    DEFF Research Database (Denmark)

    Supur, M.; Kawashima, Y.; Larsen, K. R.

    2014-01-01

    Inclusion complexes of benzo-and dithiabenzocrown ether functionalized monopyrrolotetrathiafulvalene (MPTTF) molecules were formed with Li+@C-60 (1 center dot Li+@C-60 and 2 center dot Li+@C-60). The strong complexation has been quantified by high binding constants that exceed 10(6) (-1)(M) obtai...

  7. New tris- and pentakis-fused donors containing extended tetrathiafulvalenes: New positive electrode materials for rechargeable batteries

    Directory of Open Access Journals (Sweden)

    Shintaro Iwamoto

    2015-07-01

    Full Text Available Derivatives of tris-fused TTF extended with two ethanediylidenes (5, tris- and pentakis-fused TTFs extended with two thiophene-2,5-diylidenes (6–9 were successfully synthesized. Cyclic voltammograms of the tetrakis(n-hexylthio derivative of 5 and 7 (5d, 7d consisted of two pairs of two-electron redox waves and two pairs of one-electron redox waves. On the other hand, four pairs of two-electron redox waves and two pairs of one-electron redox waves were observed for the tetrakis(n-hexylthio derivative of 9 (9d. Coin-type cells using the bis(ethylenedithio derivatives of 5 (5b, 6 (6b and the tetrakis(methylthio derivatives of 5 (5c and 8 (8c as positive electrode materials showed initial discharge capacities of 157–190 mAh g−1 and initial energy densities of 535–680 mAh g−1. The discharge capacities after 40 cycles were 64–86% of the initial discharge capacities.

  8. Structure-property relationships in redox-gated single molecule junctions - A comparison of pyrrolo-tetrathiafulvalene and viologen redox groups

    DEFF Research Database (Denmark)

    Leary, E.; Higgins, S.J.; van Zalinge, H.

    2008-01-01

    We demonstrate that the electrical 'switching" behavior of single molecules connected between two electrode contacts can be controlled by altering their structure and electrochemical characteristics. The electrical properties of gold vertical bar molecule vertical bar gold single molecule junctions...

  9. Multistimuli responsive organogels based on a new gelator featuring tetrathiafulvalene and azobenzene groups: reversible tuning of the gel-sol transition by redox reactions and light irradiation.

    Science.gov (United States)

    Wang, Cheng; Chen, Qun; Sun, Fei; Zhang, Deqing; Zhang, Guanxin; Huang, Yanyan; Zhao, Rui; Zhu, Daoben

    2010-03-10

    For the development of multistimuli responsive organogels, the new organic gelator LMWG 1, featuring electroactive TTF and photoresponsive azobenzene groups, was designed and studied. By manipulating the redox state of the TTF group in LMWG 1, the gel-sol transition for organogels with the LMWG 1 can be reversibly tuned by either chemical or electrochemical oxidation/reduction reactions. Alternatively, the photoisomerization of the azobenzene group in LMWG 1 can also trigger the gel-sol transition. Therefore, organogels with LMWG 1 respond not only to thermal stimuli but also to redox reactions and light irradiation.

  10. 2,3-[(3,6-Dioxaoctane-1,8-diylbis(sulfanediylmethylene]-6,7-bis(methylsulfanyl-1,4,5,8-tetrathiafulvalene

    Directory of Open Access Journals (Sweden)

    Rui-Bin Hou

    2009-11-01

    Full Text Available In the title molecule, C16H22S8O2, two S atoms, two O atoms and ten C atoms form a 14-membered ring with a boat conformation. In the crystal, C—H...O hydrogen bonds link the molecules into dimers which are further connected into a chain along the a axis by C—H...S hydrogen bonds.

  11. Mixed-valence, layered, cation radical salts of the ethane-bridged dimeric tetrathiafulvalene [(EDT-TTF-CH2-)2#centre dot#+] [X-][THF]0.5, X-=FeCl4-, GaCl4-

    DEFF Research Database (Denmark)

    Mézière, C.; Fourmigué, M.; Canadell, E.

    2000-01-01

    ][GaCl4] affords isostructural, mixed-valence conducting 1:1 salts [1(.+)][FeCl4-][THF](0.5) and [1(.+)][GaCl4-][THF](0.5) whose X-ray crystal structures are described. The intercalation of the tetrahedral anions within the organic slabs and the resulting sliding of the molecular diads on top of each...

  12. A new crystal structure for (BEDT–TTF)2SbF6 and some of its ...

    Indian Academy of Sciences (India)

    Unknown

    Institute of Fundamental Studies, Hantane Road, Kandy, Sri Lanka. †Department of Organic and Polymeric Materials, Tokyo Institute of Technology, O-okayama, Tokyo 152-8552, Japan. MS received 26 October 2004; revised 14 December 2004. Abstract. A new crystal structure for bis(ethylenedithio)tetrathiafulvalene ...

  13. Synthesis and Characterization of Ethylenedithio-MPTTF-PTM Radical Dyad as a Potential Neutral Radical Conductor

    DEFF Research Database (Denmark)

    Souto, Manuel; Bendixen, Dan; Jensen, Morten

    2016-01-01

    During the last years there has been a high interest in the development of new purely-organic single-component conductors. Very recently, we have reported a new neutral radical conductor based on the perchlorotriphenylmethyl (PTM) radical moiety linked to a monopyrrolo-tetrathiafulvalene (MPTTF...

  14. Comparison of ab initio molecular properties of EDO-TTF with the properties of the (EDO-TTF)(2)PF6 crystal

    NARCIS (Netherlands)

    Linker, Gerrit-Jan; van Loosdrecht, Paul H. M.; van Duijnen, Piet; Broer, Ria

    2010-01-01

    We performed ab initio quantum chemical calculations for the geometrical and electronic structure of the EDO-TTF (ethylenedioxy-tetrathiafulvalene) molecule using HF, CASSCF and DFT methods. We compare these in vacuo results with the properties of the (EDO-TTF)(2)PF6 crystal at near room

  15. Off-Planar Geometry and Structural Instability of EDO-TTF Explained by Using the Extended Debye Polarizability Model for Bond Angles

    NARCIS (Netherlands)

    Linker, Gerrit-Jan; van Duijnen, Piet Th.; van Loosdrecht, Paul H. M.; Broer-Braam, Henderika

    2012-01-01

    The geometry of ethylenedioxy-tetrathiafulvalene, EDO-TTF, plays an important role in the metal-insulator transition in the charge transfer salt (EDO-TTF)(2)PF6. The planar and off-planar geometrical conformations of the EDO-TTF molecules are explained using an extended Debye polarizability model

  16. Influence of irradiation-induced disorder on the Peierls transition in TTF-TCNQ microdomains

    DEFF Research Database (Denmark)

    Solovyeva, Vita; Cmyrev, A.; Sachser, R.

    2011-01-01

    The combined influence of electron irradiation-induced defects, substrate-induced strain and finite size effects on the electronic transport properties of individual micron-sized thin film growth domains of the organic charge transfer compound tetrathiafulvalene- tetracyanoquinodimethane (TTF-TCN...

  17. Fermi surface studies of low-dimensional organic conductors based on BEDT-TTF

    Energy Technology Data Exchange (ETDEWEB)

    Singleton, John [Department of Physics, University of Oxford, The Clarendon Laboratory, Parks Road, Oxford OX1 3PU (United Kingdom); Caulfield, Jason [Department of Physics, University of Oxford, The Clarendon Laboratory, Parks Road, Oxford OX1 3PU (United Kingdom); Hill, Stephen [Department of Physics, University of Oxford, The Clarendon Laboratory, Parks Road, Oxford OX1 3PU (United Kingdom); Blundell, Stephen [Department of Physics, University of Oxford, The Clarendon Laboratory, Parks Road, Oxford OX1 3PU (United Kingdom); Lubczynski, Wieslaw [Department of Physics, University of Oxford, The Clarendon Laboratory, Parks Road, Oxford OX1 3PU (United Kingdom); House, Andrew [Department of Physics, University of Oxford, The Clarendon Laboratory, Parks Road, Oxford OX1 3PU (United Kingdom); Hayes, William [Department of Physics, University of Oxford, The Clarendon Laboratory, Parks Road, Oxford OX1 3PU (United Kingdom); Perenboom, Jos [High Field Magnet Laboratory and Research Institute for Materials, NL 6525 ED Nijmegen (Netherlands); Kurmoo, Mohammedally [The Royal Institution, 21 Albemarle Street, London W1X 4BS (United Kingdom); Day, Peter [The Royal Institution, 21 Albemarle Street, London W1X 4BS (United Kingdom)

    1995-05-01

    This paper provides an introduction to charge-transfer salts of the ion bis(ethylenedithio)tetrathiafulvalene (ET) and their band-structure, and reviews some recent experiments on the salts involving high magnetic fields carried out by the Oxford group and coworkers. (orig.).

  18. On the association of neutral and cationic tris(tetrathiafulvaleno)dodecadehydro[18]annulenes

    DEFF Research Database (Denmark)

    Parker, Christian Richard; Rue, Kasper Lincke; Christensen, Mikkel Andreas

    2016-01-01

    Here, we report the first X-ray crystal structure of a tetrathiafulvalene-fused dehydroannulene with peripheral ethylthio substituents. In addition, we have subjected this compound to electrochemical and UV-Vis-NIR/ESR spectroelectrochemical studies to elucidate the degree to which the oxidised s...

  19. Scanning tunneling microscopy in TTF-TCNQ: Phase and amplitude modulated charge density waves

    DEFF Research Database (Denmark)

    Wang, Z.Z.; Gorard, J.C.; Pasquier, C.

    2003-01-01

    Charge density waves (CDWs) have been studied at the surface of a cleaved tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) single crystal using a low temperature scanning tunneling microscope (STM) under ultrahigh-vacuum conditions, between 300 and 33 K with molecular resolution. All CDW...

  20. Electronic structure of some β-(C10H8S8)2X compounds as studied by infrared spectroscopy

    DEFF Research Database (Denmark)

    Jacobsen, Claus Schelde; Tanner, D. B.; Williams, Jack M.

    1987-01-01

    Polarized reflectance measurements have been made on two isostructural conducting compounds of bis(ethylenedithio)tetrathiafulvalene [BEDT-TTF or ET, (C10H8S8)]: β-(ET)2AuI2 and β-(ET)2I2Br. The former is superconducting at ambient pressure with Tc=5 K, whereas the latter retains normal-metal con...

  1. Bis(1,3-dithiole) Compounds

    DEFF Research Database (Denmark)

    Andersen, Jan Rud; Engler, E. M.; Green, D. C.

    1977-01-01

    There is described the preparation of bis-1,3-dithiole compounds (I) which are key synthetic precursors for the preparation of new polymeric metal bis(dithiolene) (i.e., II) and tetrathiafulvalene compounds (i.e., III): (Image Omitted)...

  2. Defect-induced shift of the Peierls transition in TTF-TCNQ thin films

    DEFF Research Database (Denmark)

    Solovyeva, Vita; Huth, M.

    2011-01-01

    In this paper we investigate the influence of the substrate material and film thickness on the Peierls transition temperature in tetrathiafulvalene- tetracyanoquinodimethane (TTF-TCNQ) thin films, grown by physical vapor deposition. Our analysis shows that the substrate material and the growth...

  3. Metal-driven hierarchical self-assembled zigzag nanoarchitectures with electrical conductivity.

    Science.gov (United States)

    Qiao, Yan; Lin, Yiyang; Liu, Song; Zhang, Shaofei; Chen, Huanfa; Wang, Yijie; Yan, Yun; Guo, Xuefeng; Huang, Jianbin

    2013-01-25

    Quasi-one-dimensional electroactive materials with zigzag shape are fabricated by supramolecular self-assembly of a tetrathiafulvalene (TTF) derivative and metal ions under mild conditions. This is the first time that self-assembled organic conductors with zigzag shape are reported.

  4. Use of solvent to regulate the degree of polymerisation in weakly associated supramolecular oligomers

    DEFF Research Database (Denmark)

    Bähring, Steffen; Kim, D. S.; Duedal, T.

    2014-01-01

    Using a tetrathiafulvalene functionalised calix[4] pyrrole (TTF-C[4]P; 1) and alkyl diester-linked bis-dinitrophenols (2-4), it was found that the solvent polarity and linker length have an effect on the molecular aggregation behaviour. 2D H-1 NOESY, DOSY NMR and UV-vis-NIR spectroscopic studies...

  5. Organic Metals

    DEFF Research Database (Denmark)

    Andersen, Jan Rud; Craven, R. A.; Weidenborner, J. E.

    1977-01-01

    Replacement of the sulphur atoms in the charge transfer salt tetrathiafulvalene (TTF)–2,5-diethyltetracyano-p-quinodimethane (DETCNQ) with selenium yields the isostructural and better conducting analogue tetraselenafulvalene (TSeF)–DETCNQ, in which the Peierls transition temperature is decreased....

  6. Far-Infrared Study of the Charge Density Wave in Tetrathiofulvalene Tetracyanoquinodimethane (TTF-TCNQ)

    DEFF Research Database (Denmark)

    Tanner, D. B.; Cummings, K. D.; Jacobsen, Claus Schelde

    1981-01-01

    Detailed far-infrared measurements at temperatures from 25 to 300 K provide strong support for a charge-density-wave mechanism for the dc conductivity and microwave dielectric constant of tetrathiafulvalene tetracyanoquinodimethane (TTF-TCNQ). At low temperatures the charge-density wave is pinned...

  7. Rational Control of Electronic Structure and Lattice Architecture in Electrically Conducting Molecular/Macromolecular Assemblies.

    Science.gov (United States)

    1981-12-23

    partial oxidation (6+) follows from this information and the stoichiometry. As an example, nickel phthalocyanine iodide, (Ni(Pc)]1lI , crystallizes in...tetrathiafulvalene: TMTTF tetramethyttetrathiafulvalette; TTT - tetrathiatetracene; M(OEP) " 2,3,7,8,12,13,17,18- octaethylporphyrin . donor systems known to...Partially Oxidized Nickel and Palladium Bisdiphenylglyoximates," J. Am. Chem. Soc., 101, 2921 (1979), and referen- ces therein. 18. T. J. Marks, D. F. Webster

  8. A tristable [2]pseudo[2]rotaxane

    KAUST Repository

    Trabolsi, Ali

    2010-01-01

    A strategy towards increasing the lifetime of the metastable state of a [2]rotaxane incorporating tetrathiafulvalene, 1,5-dioxynaphthalene and bipyridinium (BIPY 2+) is presented. Incorporation of BIPY 2+ served multiple roles as an electrostatic barrier to relaxation, a supramolecular recognition site for bis-1,5-dioxynaphthalene[38]crown-10 macrocycle, and upon reduction a recognition site for the mechanically bonded cyclobis(paraquat-p-phenylene) ring. © The Royal Society of Chemistry 2010.

  9. Ambient-pressure organic superconductor

    Science.gov (United States)

    Williams, Jack M.; Wang, Hsien-Hau; Beno, Mark A.

    1986-01-01

    A new class of organic superconductors having the formula (ET).sub.2 MX.sub.2 wherein ET represents bis(ethylenedithio)-tetrathiafulvalene, M is a metal such as Au, Ag, In, Tl, Rb, Pd and the like and X is a halide. The superconductor (ET).sub.2 AuI.sub.2 exhibits a transition temperature of 5 K which is high for organic superconductors.

  10. Polythiophene and oligothiophene systems modified by TTF electroactive units for organic electronics.

    Science.gov (United States)

    Kanibolotsky, Alexander L; Findlay, Neil J; Skabara, Peter J

    2015-01-01

    The aim of this review is to give an update on current progress in the synthesis, properties and applications of thiophene-based conjugated systems bearing tetrathiafulvalene (TTF) units. We focus mostly on the synthesis of poly- and oligothiophenes with TTF moieties fused to the thiophene units of the conjugated backbone either directly or via a dithiin ring. The electrochemical behaviour of these materials and structure-property relationships are discussed. The study is directed towards the development of a new type of organic semiconductors based on these hybrid materials for application in organic field effect transistors and solar cells.

  11. Lowering Band Gap of an Electroactive Metal-Organic Framework via Complementary Guest Intercalation.

    Science.gov (United States)

    Guo, Zhiyong; Panda, Dillip K; Gordillo, Monica A; Khatun, Amina; Wu, Hui; Zhou, Wei; Saha, Sourav

    2017-09-27

    A new honeycomb-shaped electroactive metal-organic framework (MOF) has been constructed from an electron deficient naphthalenediimide (NDI) ligand equipped with two terminal salicylic acid groups. π-Intercalation of electron-rich planar tetrathiafulvalene (TTF) guests between the NDI ligands stacked along the walls lowers the electronic band gap of the material by ca. 1 eV. An improved electron delocalization through the guest-mediated π-donor/acceptor stacks is attributed to the diminished band gap of the doped material, which forecasts an improved electrical conductivity.

  12. Enhanced detection of explosives by turn-on resonance Raman upon host-guest complexation in solution and the solid state

    DEFF Research Database (Denmark)

    Witlicki, Edward H.; Bähring, Steffen; Johnsen, Carsten

    2017-01-01

    complexation occur via a mechanism of resonance between the 785 nm laser line and the strongly absorbing charge-transfer chromophore arising from the complex between electron-donating TTF-C[4]P and electron-accepting nitroaromatic explosives. The addition of chloride forms the Cl-·TTF-C[4]P complex resetting......The recognition of nitroaromatic explosives by a tetrakis-tetrathiafulvalene-calix[4]pyrrole receptor (TTF-C[4]P) yields a "turn on" and fingerprinting response in the resonance Raman scattering observed in solution and the solid state. Intensity changes in nitro vibrations with analyte...

  13. Polythiophene and oligothiophene systems modified by TTF electroactive units for organic electronics

    Directory of Open Access Journals (Sweden)

    Alexander L. Kanibolotsky

    2015-09-01

    Full Text Available The aim of this review is to give an update on current progress in the synthesis, properties and applications of thiophene-based conjugated systems bearing tetrathiafulvalene (TTF units. We focus mostly on the synthesis of poly- and oligothiophenes with TTF moieties fused to the thiophene units of the conjugated backbone either directly or via a dithiin ring. The electrochemical behaviour of these materials and structure–property relationships are discussed. The study is directed towards the development of a new type of organic semiconductors based on these hybrid materials for application in organic field effect transistors and solar cells.

  14. Comparison of ab initio molecular properties of EDO-TTF with the properties of the (EDO-TTF) 2PF 6 crystal

    Science.gov (United States)

    Linker, Gerrit-Jan; Loosdrecht, Paul H. M. van; Duijnen, Piet van; Broer, Ria

    2010-03-01

    We performed ab initio quantum chemical calculations for the geometrical and electronic structure of the EDO-TTF (ethylenedioxy-tetrathiafulvalene) molecule using HF, CASSCF and DFT methods. We compare these in vacuo results with the properties of the (EDO-TTF) 2PF 6 crystal at near room temperature. We demonstrate that, by bending and charging the molecule in vacuum, the deformation that is thought to be the origin of charge ordering in this material is an inherent property of the EDO-TTF molecule. We further show that deformations can be readily made at ambient temperatures.

  15. Physical Properties of Some ET-Based Organic Metals and Superconductors with Mercury Containing Anions

    Science.gov (United States)

    Lyubovskii, R. B.; Lyubovskaya, R. N.; Dyachenko, O. A.

    1996-12-01

    Because of mercury atoms capability of forming the compounds with various coordination, the application of the electrolytes with Hg containing anions in electrochemical oxidation of ET (bis(ethylenedithio)tetrathiafulvalene) results in the formation of ET salts with the anions of different composition. The properties of organic metals and superconductors are briefly described for three families: 1) ET4Hg{3-δ}X8 ((δ 0, and a series of other peculiarities. Shubnikov-de Haas oscillations were observed for some salts of (ET)8[ Hg4X{12}(C6H5Y)2] family. The possible types of Fermi surface are discussed for these salts.

  16. Synthesis and Studies of Sulfur-Containing Heterocyclic Molecules for Molecular Electronics

    DEFF Research Database (Denmark)

    Mazzanti, Virginia

    the synthesis of dimeric structures of redox active system tetrathiafulvalene (TTF). Molecules with different conjugation pathways bridging two TTFs were synthesized and studied using CV and DPV in order to probe the electronic interaction between these two redox units. The last aspect of this thesis, which......This work describes the synthesis and studies of sulfur containing π conjugated heterocycles, which are considered interesting motifs in the field of molecular electronics. The first project, which is covered in Chapter 1, concerns the functionalization of tetracycle dibenzo[bc,fg][1...

  17. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali

    2009-12-17

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  18. Collective concerted motion in a molecular adlayer visualized through the surface diffusion of isolated vacancies

    Science.gov (United States)

    Urban, Christian; Otero, Roberto; Écija, David; Trelka, Marta; Martín, Nazario; Gallego, José M.; Miranda, Rodolfo

    2016-10-01

    We have measured STM movies to study the diffusion of individual vacancies in a self-assembled layer of a tetrathiafulvalene derivative (exTTF) on Au(111) at room temperature. The diffusion is anisotropic, being faster along the compact direction of the molecular lattice. A detailed analysis of the anisotropic displacement distribution of the single vacancies shows that the relative abundance of double jumps (that is, the collective motion of molecular dimers) with respect to single jumps is rather large, the number of double jumps being more than 20% of the diffusion events. We conjecture that the relative abundances of long jumps might be related to the strength of the intermolecular bonding and the misfit of the molecular overlayer with the substrate lattice.

  19. Molecular junctions based on SAMs of cruciform oligo(phenylene ethynylene)s

    DEFF Research Database (Denmark)

    Wei, Zhongming; Li, Tao; Jennum, Karsten Stein

    2012-01-01

    Cruciform oligo(phenylene ethynylene)s (OPEs) with an extended tetrathiafulvalene (TTF) donor moiety (OPE5-TTF and OPE3-TTF) and their simple analogues (OPE5-S and OPE3) without conjugated substituents were used to form high quality self-assembled monolayers (SAMs) on ultra-flat gold substrates....... Molecular junctions based on these SAMs were investigated using conducting-probe atomic force microscopy (CP-AFM). The TTF substituent changes the molecular orbital energy levels and decreases the HOMO-LUMO energy gap, resulting in a nine-fold increase in conductance for both TTF cruciform OPEs compared...... to the unsubstituted analogues. The difference in electrical transport properties of the SAMs was reproduced by the theoretical transport calculations for the single molecules....

  20. Modulating the electronic and optical properties of monolayer arsenene phases by organic molecular doping

    Science.gov (United States)

    Singh, Deobrat; Gupta, Sanjeev K.; Sonvane, Yogesh; Sahoo, Satyaprakash

    2017-12-01

    Recently, arsenene monolayer structure of the arsenic with two phases has displayed semiconducting behavior. We have systematically investigated the electronic and optical properties of single-layer arsenene with two types of functionalized organic molecules; an electrophilic molecule [tetracyanoquinodimethane (TCNQ)] and a nucleophilic molecule [tetrathiafulvalene (TTF)], as an electron acceptor and electron donor, respectively. The interfacial charge transfer between the arsenene monolayer and TCNQ/TTF molecules extensively reduces the band gap of arsenene and accordingly resulted in a p- or n-type semiconducting behavior, respectively. We have also performed the interfacial charge transfer from organic molecules to monolayer arsenene and vice versa. The interfacial surface molecular modification has established an efficient way to develop the light harvesting of arsenene in different polarization directions. Our theoretical investigation suggests that such n- and p-type arsenene semiconductors would broaden the applications in the field of nanoelectronic and optoelectronic devices such as photodiodes and it is also useful for constructing functional electronic systems.

  1. Single-Molecule Electrochemical Gating in Ionic Liquids

    DEFF Research Database (Denmark)

    Kay, Nicola J.; Higgins, Simon J.; Jeppesen, Jan O.

    2012-01-01

    The single-molecular conductance of a redox active molecular bridge has been studied in an electrochemical single-molecule transistor configuration in a room-temperature ionic liquid (RTIL). The redox active pyrrolo-tetrathiafulvalene (pTTF) moiety was attached to gold contacts at both ends through...... −(CH2)6S– groups, and gating of the redox state was achieved with the electrochemical potential. The water-free, room-temperature, ionic liquid environment enabled both the monocationic and the previously inaccessible dicationic redox states of the pTTF moiety to be studied in the in situ scanning...... relaxation. Using this view, reorganization energies of ∼1.2 eV have been estimated for both the first and second redox transitions for the pTTF bridge in the 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BMIOTf) ionic liquid environment. By contrast, in aqueous environments, a much smaller...

  2. Understanding the Influence of the Electronic Structure on the Crystal Structure of a TTF-PTM Radical Dyad.

    Science.gov (United States)

    Vela, Sergi; Souto, Manuel; Ratera, Imma; Rovira, Concepció; Veciana, Jaume

    2016-12-29

    The understanding of the crystal structure of organic compounds, and its relationship to their physical properties, have become essential to design new advanced molecular materials. In this context, we present a computational study devoted to rationalize the different crystal packing displayed by two closely related organic systems based on the TTF-PTM dyad (TTF = tetrathiafulvalene, PTM = polychlorotriphenylmethane) with almost the same molecular structure but a different electronic one. The radical species (1), with an enhanced electronic donor-acceptor character, exhibits a herringbone packing, whereas the nonradical protonated analogue (2) is organized forming dimers. The stability of the possible polymorphs is analyzed in terms of the cohesion energy of the unit cell, intermolecular interactions between pairs, and molecular flexibility of the dyad molecules. It is observed that the higher electron delocalization in radical compound 1 has a direct influence on the geometry of the molecule, which seems to dictate its preferential crystal structure.

  3. One-Pot Synthesis of Cu(II Complex with Partially Oxidized TTF Moieties

    Directory of Open Access Journals (Sweden)

    Hiroki Oshio

    2012-07-01

    Full Text Available The one-pot synthesis of a Cu(II complex with partially oxidized tetrathiafulvalene (TTF moieties in its capping MT-Hsae-TTF ligands, [CuII(MT-sae-TTF2] [CuICl2] was realized by the simultaneous occurrence of Cu(II complexation and CuIICl2 mediated oxidation of TTF moieties. The crystal structure was composed of one-dimensional columns formed by partially oxidized TTF moieties and thus the cation radical salt showed relatively high electrical conductivity. Tight binding band structure calculations indicated the existence of a Peierls gap due to the tetramerization of the TTF moieties in the one-dimensional stacking column at room temperature, which is consistent with the semiconducting behavior of this salt.

  4. Molecular heterojunctions of oligo(phenylene ethynylene)s with linear to cruciform framework

    DEFF Research Database (Denmark)

    Wei, Zhongming; Hansen, Tim; Santella, Marco

    2015-01-01

    Electrical transport properties of molecular junctions are fundamentally affected by the energy alignment between molecular frontier orbitals (highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO)) and Fermi level (or work function) of electrode metals....... Dithiafulvene (DTF) is used as substituent group to the oligo(phenylene ethynylene) (OPE) molecular wires and different molecular structures based on OPE3 backbone (with linear to cruciform framework) are achieved, with viable molecular orbitals and HOMO-LUMO energy gaps. OPE3, OPE3-DTF, and OPE3......-tetrathiafulvalene (TTF) can form good self-assembled monolayers (SAMs) on Au substrates. Molecular heterojunctions based on these SAMs are investigated using conducting probe-atomic force microscopy with different tips (Ag, Au, and Pt) and Fermi levels. The calibrated conductance values follow the sequence OPE3-TTF...

  5. Synthesis of covalently linked oligo(phenyleneethynylene) wires incorporating dithiafulvene units

    DEFF Research Database (Denmark)

    Jørgensen, Frederik Præstholm; Petersen, Johannes Fabritius; Andersen, Cecilie Lindholm

    2017-01-01

    Controlled alignment and self-assembly of molecular wires is one of the challenges in the field of molecular electronics. Here, we take an approach by which two oligo(phenyleneethynylene)s (OPEs) are linked together through one vinylogous linker. These molecules thus incorporate a central stilbene...... part from which the two OPE wires propagate in a so-called "H-cruciform"-like motif. Each ring of the central stilbene unit also contains a redox-active dithiafulvene (DTF) unit and this part of the molecule can thus be considered as an extended tetrathiafulvalene (TTF). Here, we present how such H...... by subjecting a differentially protected diethynyl-substituted derivative of terephthalaldehyde to a phosphite-mediated coupling reaction in the presence of a 1,3-dithiol-2-thione. This reaction forms the central stilbene-extended TTF with alkyne substituents and relies on an "umpolung" of the para substituents...

  6. Molecular Electronics

    DEFF Research Database (Denmark)

    Jennum, Karsten Stein

    This thesis includes the synthesis and characterisation of organic compounds designed for molecular electronics. The synthesised organic molecules are mainly based on two motifs, the obigo(phenyleneethynylenes) (OPE)s and tetrathiafulvalene (TTF) as shown below. These two scaffolds (OPE and TTF...... transistors (Part 2). The synthetic protocols rely on stepwise Sonogashira coupling reactions. Conductivity studies on various OPE-based molecular wires reveal that mere OPE compounds have a higher electrical resistance compared to the cruciform based wires (up to 9 times higher). The most spectacular result...... be potential candidates for future molecular electronics Synthesis of a new donor-acceptor chromophore based on a benzoquinone- TTF motif (QuinoneDTF) is also described herein (Part 2). Reaction of this molecule with acid induces a colour change from purple to orange. The purple colour can be restored...

  7. Dual enzymatic biosensor for simultaneous amperometric determination of histamine and putrescine.

    Science.gov (United States)

    Henao-Escobar, W; Del Torno-de Román, L; Domínguez-Renedo, O; Alonso-Lomillo, M A; Arcos-Martínez, M J

    2016-01-01

    A disposable electrodic system consisting of two working electrodes connected in array mode has been developed for the simultaneous determination of histamine (His) and putrescine (Put). Histamine deshydrogenase and putrescine oxidase enzymes were respectively immobilized by crosslinking on each working screen-printed electrode, both modified with tetrathiafulvalene. The dual system allowed the simultaneous amperometric determination of both species by measuring the oxidation current of the mediator in each working electrode. The effect of other potentially interfering biogenic amines was also evaluated. The capability of detection was of 8.1 ± 0.7 for His and 10 ± 0.6 μM for Put. The precision in terms of relative standard deviation was of 3.5% and 6.7% for His and Put, respectively. The developed biosensor was successfully applied to the determination of His and Put in different food samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Resonant inelastic x-ray scattering probes the electron-phonon coupling in the spin liquid κ -(BEDT-TTF)2Cu2(CN) 3

    Science.gov (United States)

    Ilakovac, V.; Carniato, S.; Foury-Leylekian, P.; Tomić, S.; Pouget, J.-P.; Lazić, P.; Joly, Y.; Miyagawa, K.; Kanoda, K.; Nicolaou, A.

    2017-11-01

    Resonant inelastic x-ray scattering at the N K edge reveals clearly resolved harmonics of the anion plane vibrations in the κ -(BEDT-TTF) 2Cu2 (CN) 3 spin-liquid insulator. Tuning the incoming light energy at the K edge of two distinct N sites permits us to excite different sets of phonon modes. The cyanide (CN) stretching mode is selected at the edge of the ordered N sites which are more strongly connected to the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) molecules, while positionally disordered N sites show multimode excitation. Combining measurements with calculations on an anion plane cluster permits us to estimate the site-dependent electron-phonon coupling of the modes related to nitrogen excitation.

  9. Isotope effect on metal-insulator transition of (EDO-TTF) 2XF 6 (X = P, As) with multi-instability of metallic state

    Science.gov (United States)

    Nakano, Yoshiaki; Balodis, Karlis; Yamochi, Hideki; Saito, Gunzi; Uruichi, Mikio; Yakushi, Kyuya

    2008-12-01

    The partially deuterated 4,5-ethylenedioxy-tetrathiafulvalene- d2 (EDO-TTF- d2) was synthesized from the undeuterated EDO-TTF- d0. The single crystals of (EDO-TTF- d2) 2XF 6 (X = P, As) were prepared by the conventional electrocrystallization technique. The deuterium contents of EDO-TTF- d2 itself and the radical cation salts were 99% D by mass spectral analysis. The magnetic susceptibility measurement revealed that (EDO-TTF- d2) 2XF 6 undergoes a metal-insulator transition at 2-3 K higher temperature than the undeuterated salts. In infrared and Raman spectra, significant isotope shifts were observed not only on C-H vibrational modes but also on TTF-skeletal modes. The assignment of experimental bands was performed on the basis of normal-mode analysis at B3LYP/6-31G(d,p) level of theory.

  10. Off-planar geometry and structural instability of EDO-TTF explained by using the extended debye polarizability model for bond angles.

    Science.gov (United States)

    Linker, Gerrit-Jan; van Duijnen, Piet Th; van Loosdrecht, Paul H M; Broer, Ria

    2012-07-05

    The geometry of ethylenedioxy-tetrathiafulvalene, EDO-TTF, plays an important role in the metal-insulator transition in the charge transfer salt (EDO-TTF)(2)PF(6). The planar and off-planar geometrical conformations of the EDO-TTF molecules are explained using an extended Debye polarizability model for the bond angle. The geometrical structure of EDO-TTF is dictated by its four sulfur bond angles and these are, in turn, determined by the polarizability of the sulfur atoms. With Hartree-Fock and second-order Møller-Plesset perturbation theory calculations on EDO-TTF, TTF, H(2)S, and their oxygen and selenium substituted counterparts we confirm this hypothesis. The Debye polarizability model for bond angles relates directly the optimum bond angle with the polarizability of the center atom. Considering the (EDO-TTF)(2)PF(6) material in this light proves to be very fruitful.

  11. Synthesis and Studies of Sulfur-Containing Heterocyclic Molecules for Molecular Electronics

    DEFF Research Database (Denmark)

    Mazzanti, Virginia

    This work describes the synthesis and studies of sulfur containing π conjugated heterocycles, which are considered interesting motifs in the field of molecular electronics. The first project, which is covered in Chapter 1, concerns the functionalization of tetracycle dibenzo[bc,fg][1......,4]dithiapentalene (DDP). Attempts to prepare the S-O analog are also discussed. Chapter 2, focuses upon the studies performed on DDP and other sulfur containing π conjugated organic molecules. Organic Field Effect Transistor devices were fabricated and their performances were evaluated. Chapter 3 entails...... the synthesis of dimeric structures of redox active system tetrathiafulvalene (TTF). Molecules with different conjugation pathways bridging two TTFs were synthesized and studied using CV and DPV in order to probe the electronic interaction between these two redox units. The last aspect of this thesis, which...

  12. Guided assembly of metal and hybrid conductive probes using floating potential dielectrophoresis.

    Science.gov (United States)

    Puigmartí-Luis, Josep; Stadler, Johannes; Schaffhauser, Daniel; del Pino, Angel Pérez; Burg, Brian R; Dittrich, Petra S

    2011-03-01

    We present the site-selective, parallel and reproducible formation of conductive gold and tetrathiafulvalene-gold (TTF-Au) hybrid micro- and nanowires from their respective ion salt and cation-radical solutions. While the formation of micro- and nanowires by means of dielectrophoresis with directly coupled electrodes has been thoroughly investigated in recent studies, we present here the first relevant example of metal and hybrid wire assembly obtained by floating potential dielectrophoresis. In this configuration, the assembly of micro- and nanowires is achieved by capacitively coupling a large electrode (bias electrode) to a conductive substrate (p-doped Si) separated by an insulating oxide layer. In contrast to former studies, this allows parallel production of micro- and nanowires with only one pair of electrodes connected to a sine wave generator. We further demonstrate that these structures are suitable probes for localized surface enhanced Raman spectroscopy (SERS).

  13. Evaluating the Performance of DFT Functionals in Assessing the Interaction Energy and Ground-State Charge Transfer of Donor/Acceptor Complexes: Tetrathiafulvalene−Tetracyanoquinodimethane (TTF−TCNQ) as a Model Case

    KAUST Repository

    Sini, Gjergji

    2011-03-08

    We have evaluated the performance of several density functional theory (DFT) functionals for the description of the ground-state electronic structure and charge transfer in donor/acceptor complexes. The tetrathiafulvalene- tetracyanoquinodimethane (TTF-TCNQ) complex has been considered as a model test case. Hybrid functionals have been chosen together with recently proposed long-range corrected functionals (ωB97X, ωB97X-D, LRC-ωPBEh, and LC-ωPBE) in order to assess the sensitivity of the results to the treatment and magnitude of exact exchange. The results show an approximately linear dependence of the ground-state charge transfer with the HOMO TTF-LUMOTCNQ energy gap, which in turn depends linearly on the percentage of exact exchange in the functional. The reliability of ground-state charge transfer values calculated in the framework of a monodeterminantal DFT approach was also examined. © 2011 American Chemical Society.

  14. Surface-Enhanced Raman Spectroelectrochemistry of TTF-Modified Self-Assembled Monolayers.

    Science.gov (United States)

    Paxton, Walter F; Kleinman, Samuel L; Basuray, Ashish N; Stoddart, J Fraser; Van Duyne, Richard P

    2011-05-19

    Surface-enhanced Raman spectroscopy (SERS) was used to monitor the response of a self-assembled monolayer (SAM) of a tetrathiafulvalene (TTF) derivative on a gold film-over-nanosphere electrode. The electrochemical response observed was rationalized in terms of the interactions between TTF moieties as the oxidation state was changed. Electrochemical oxidation to form the monocation caused the absorbance of the TTF unit to coincide with both the laser excitation wavelength and the localized surface plasmon resonance (LSPR), resulting in surface-enhanced resonance Raman scattering (SERRS). The vibrational frequency changes that accompany electron transfer afford a high-contrast mechanism that can be used to determine the oxidation state of the TTF unit in an unambiguous manner.

  15. Terahertz-Field-Induced Large Macroscopic Polarization and Domain-Wall Dynamics in an Organic Molecular Dielectric.

    Science.gov (United States)

    Morimoto, T; Miyamoto, T; Yamakawa, H; Terashige, T; Ono, T; Kida, N; Okamoto, H

    2017-03-10

    A rapid polarization control in paraelectric materials is important for an ultrafast optical switching useful in the future optical communication. In this study, we applied terahertz-pump second-harmonic-generation-probe and optical-reflectivity-probe spectroscopies to the paraelectric neutral phase of an organic molecular dielectric, tetrathiafulvalene-p-chloranil and revealed that a terahertz pulse with the electric-field amplitude of ∼400  kV/cm produces in the subpicosecond time scale a large macroscopic polarization whose magnitude reaches ∼20% of that in the ferroelectric ionic phase. Such a large polarization generation is attributed to the intermolecular charge transfers and breathing motions of domain walls between microscopic neutral and ionic domains induced by the terahertz electric field.

  16. Physical Properties and Dimensionality of κ-(BEDT-TTF)2Cu(CN)[N(CN)2

    Science.gov (United States)

    Nakamura, Toshikazu; Komatsu, Tokutaro; Saito, Gunzi; Osada, Toshihito; Kagoshima, Seiichi; Miura, Noboru; Kato, Kiyonori; Maruyama, Yusei; Oshima, Kokichi

    1993-12-01

    The electrical resistivity measurements for the novel organic superconductor κ-(BEDT-TTF)2Cu(CN)[N(CN)2] (Tc{=}11.2 K) [BEDT-TTF represents bis (ethylenedithiolo)tetrathiafulvalene] under pressure or in high magnetic field were studied. Several physical parameters, such as the superconducting transition temperature (Tc), the depressibility of Tc with pressure (-dTc/dP), the residual resistance ratio (RRR), the upper critical field (HC2), and the effective Ginzburg-Landau mass anisotropy between perpendicular and parallel to the conducting plane (m///m\\bot), are determined. They are discussed in comparison with those of other κ-type organic superconductors with Tc above 10 K; κ-(BEDT-TTF)2Cu(NCS)2 and κ-(BEDT-TTF)2Cu[N(CN)2]Br. A simple relation was observed between these parameters (Tc, -dTc/dP and RRR) and the dimensionality of the electronic structures of these superconductors.

  17. Functionally rigid bistable [2]rotaxanes

    DEFF Research Database (Denmark)

    Nygaard, Sune; Leung, Ken C-F; Aprahamian, Ivan

    2007-01-01

    component resides, to all intents and purposes, predominantly on the MPTTF unit in the ground state. As a consequence of these two effects, the assignment of NMR and UV-vis data is more simplified as compared to previous donor-acceptor bistable [2]rotaxanes. This development has not only allowed for much......Two-station [2]rotaxanes in the shape of a degenerate naphthalene (NP) shuttle and a nondegenerate monopyrrolotetrathiafulvalene (MPTTF)/NP redox-controllable switch have been synthesized and characterized in solution. Their dumbbell-shaped components are composed of polyether chains interrupted......-free bistable [2]rotaxane. Utilization of MPTTF removes the cis/trans isomerization that characterizes the tetrathiafulvalene (TTF) parent core structure. Furthermore, only one translational isomer is observed (> 95

  18. A Novel Extended N-Methyl Monopyrrolotetrathiafulvalene Based on 2-Methylene-4,5-Bis(Methylthio-1,3-Dithiole

    Directory of Open Access Journals (Sweden)

    Ruibin Hou

    2014-12-01

    Full Text Available The title compound was prepared via a cross-coupling reaction and its crystal structure has been determined. It crystallized in the triclinic space group P-1 with cell parameters: a = 8.552(2 Å, b = 11.310(2 Å, c = 16.150(3 Å, α = 109.55(3°, β = 91.45(3°, γ = 91.28(3°, V = 1470.6(5 Å3, Z = 2 at 296 K. There is one molecule in the asymmetric unit. In the crystal structure, the neighboring molecules from dimers by weak intermolecular π···π interactions between the pyrrole and tetrathiafulvalene units. The dimers are further linked through C-H···π interactions to generate one-dimensional chains along the [100] direction. The arrangement of the molecules corresponds to an overlap between the HOMO and LUMO.

  19. Hydrogen bonded anion ribbons, networks and clusters and sulfur-anion interactions in novel radical cation salts of BEDT-TTF with sulfamate, pentaborate and bromide.

    Science.gov (United States)

    Brooks, Andrew C; Martin, Lee; Day, Peter; Lopes, Elsa B; Almeida, Manuel; Kikuchi, Koichi; Fujita, Wataru; Sasamori, Kota; Aktusu, Hiroki; Wallis, John D

    2013-05-14

    The novel radical cation salt (BEDT-TTF)3(sulfamate)2·2H2O (BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene) is semiconducting with donor stacks comprised of pairs of partially oxidized molecules and a single more highly oxidized molecule which is twisted out of the stack by ca. 30°. Hydrogen bonded pairs of sulfamate ions are linked into parallel ribbons by further hydrogen bonding between sulfamates and bridging water molecules. In contrast, the BEDT-TTF salt with pentaborate contains infinite layers formed of a network of hydrogen bonded pentaborate anions. Two new bromide salts of BEDT-TTF are reported, one is a semiconducting 1 : 1 salt in which the bromide is integrated among the BEDT-TTF donors, while the other contain a square of four bromide ions linked together by hydrogen bonding to a centrally located H5O2(+) cation for every five BEDT-TTF molecules.

  20. Insulator-metal transitions induced by electric field and photoirradiation in organic Mott insulator deuterated κ-(BEDT-TTF)2Cu[N(CN)2]Br.

    Science.gov (United States)

    Sabeth, Farzana; Iimori, Toshifumi; Ohta, Nobuhiro

    2012-04-25

    The Mott insulator-metal transition induced by an external stimulus such as electric field, pressure, chemical doping, or photoirradiation has received considerable attention because of the potential use in new optoelectronic functional devices. Here we report an abrupt Mott insulator-metal transition observed as a current jump in a molecular-based Mott insulator, namely, deuterated κ-(BEDT-TTF)(2)Cu[N(CN)(2)]Br, where BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene, upon application of a pulsed voltage of certain magnitude (threshold voltage). Furthermore, the threshold voltage needed for the transition is shown to be reduced by photoirradiation. Thus, the Mott insulator-metal transition can be controlled by a combination of an external electric field and photoirradiation.

  1. Protonated paramagnetic redox forms of di-o-quinone bridged with p-phenylene-extended TTF: A EPR spectroscopy study

    Directory of Open Access Journals (Sweden)

    Nikolay O. Chalkov

    2016-11-01

    Full Text Available The chemical oxidation and reduction processes of deprotonated, direduced o-quinone-exTTF-o-quinone in protic solvents were studied by EPR spectroscopy. The formation of relatively stable paramagnetic protonated redox forms of the parent triad was very surprising. The character of spin-density distribution in the semiquinone–quinone and semiquinone–catechol redox forms indicates that the p-phenylene-extended tetrathiafulvalene connector provides a quite effective electronic communication channel between dioxolene coordination sites. It was found that the deprotonated, direduced o-quinone-exTTF-o-quinone is capable to reduction of the metal copper in solution. The radical anion species formed in this reaction exists in solution as a solvent-separated ion pair with a copper cation. A character of spin-density distribution in a radical anion species leads to the conclusion that the ligand corresponds to type III of the Robin–Day classification.

  2. Protonated paramagnetic redox forms of di-o-quinone bridged with p-phenylene-extended TTF: A EPR spectroscopy study.

    Science.gov (United States)

    Chalkov, Nikolay O; Cherkasov, Vladimir K; Abakumov, Gleb A; Starikov, Andrey G; Kuropatov, Viacheslav A

    2016-01-01

    The chemical oxidation and reduction processes of deprotonated, direduced o-quinone-exTTF-o-quinone in protic solvents were studied by EPR spectroscopy. The formation of relatively stable paramagnetic protonated redox forms of the parent triad was very surprising. The character of spin-density distribution in the semiquinone-quinone and semiquinone-catechol redox forms indicates that the p-phenylene-extended tetrathiafulvalene connector provides a quite effective electronic communication channel between dioxolene coordination sites. It was found that the deprotonated, direduced o-quinone-exTTF-o-quinone is capable to reduction of the metal copper in solution. The radical anion species formed in this reaction exists in solution as a solvent-separated ion pair with a copper cation. A character of spin-density distribution in a radical anion species leads to the conclusion that the ligand corresponds to type III of the Robin-Day classification.

  3. Spin-frustrated antiferromagnets based on BEDT-TTF and manganese dicyanamide complexes

    Science.gov (United States)

    Morgunov, R. B.; Kurganova, E. V.; Tanimoto, Y.; Markosyan, A. S.; Kazakova, A. V.; Kushch, N. D.; Yagubskiĭ, É. B.; Dubrovskiĭ, A. D.; Shilov, G. V.

    2007-05-01

    The magnetic properties of new radical cation salts ( BEDT-TTF)2[CuMn( dca)4] ( I) and ( BEDT-TTF)2[Mn( dca)3] ( II) [where BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene and dca = N(CN2)] are investigated using superconducting quantum interference device (SQUID) magnetometry and electron paramagnetic resonance (EPR) spectroscopy. It is established that, at temperatures below 25 K, both salts are characterized by antiferromagnetic deviations from the paramagnetic behavior. The Weiss constants for compounds I and II are determined to be -5 and -10 K, respectively. The corresponding correlations in the structure of compound I are short-range correlations and do not lead to a change in the effective spin equal to 5/2. It is found that the widths of the EPR lines attributed to the BEDT-TTF conducting sublattice correlate with the widths of the EPR lines associated with the magnetic sublattice of the Mn( dca){3/-} counterion in the structure of salt II. This correlation suggests that the antiferromagnetic ordering in the magnetic sublattice of compound II affects the spin-lattice relaxation in the BEDT-TTF sublattice. The dependence of the magnetic moment on the magnetic field for compound II at a temperature of 2 K is typical of weakly frustrated uniaxial antiferromagnets and exhibits a kink in a magnetic field of 20 kOe, which corresponds to spin-flop transitions.

  4. Implementation of a new integrated d-lactic acid biosensor in a semiautomatic FIA system for the simultaneous determination of lactic acid enantiomers. Application to the analysis of beer samples.

    Science.gov (United States)

    Vargas, E; Ruiz, M A; Campuzano, S; González de Rivera, G; López-Colino, F; Reviejo, A J; Pingarrón, J M

    2016-05-15

    An integrated amperometric d-lactic acid biosensor involving a gold film deposited by sputtering on a stainless steel disk electrode where the enzymes D-lactic acid dehydrogenase (DLDH) and diaphorase (DP) as well as the redox mediator tetrathiafulvalene (TTF) are coimmobilized by using a dialysis membrane, is reported in this work. Amperometry in stirred solutions at a detection potential of +0.15 V (vs Ag/AgCl reference electrode) provided a linear calibration plot for D-lactic acid over the 1.0×10(-4) to 3.8×10(-3) g L(-1) concentration range, with a limit of detection of 3.1×10(-5) g L(-1). The usefulness of the biosensor was demonstrated by determining D-lactic acid in beer samples with good results. Additionally, the biosensor was implemented together with a commercial L-lactic amperometric biosensor in a semiautomatic flow-injection analysis (FIA) system able to perform a rapid and simple stereo-specific determination of D- and D-lactic without a previous separation step. The operational characteristics of the biosensors under flow conditions were evaluated and its applicability was demonstrated through the simultaneous determination of both enantiomers in beer samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Automatic bionalyzer using an integrated amperometric biosensor for the determination of L-malic acid in wines.

    Science.gov (United States)

    Vargas, E; Ruiz, M A; Ferrero, F J; Campuzano, S; Ruiz-Valdepeñas Montiel, V; Reviejo, A J; Pingarrón, J M

    2016-09-01

    A new automatic bioanalyzer for L-malic acid using an integrated amperometric biosensor as detector is reported for the first time in this work. The biosensor is constructed by gold film sputtering deposition on a stainless steel disk electrode and co-immobilization of the enzymes malate dehydrogenase (MDH) and diaphorase (DP) together with the redox mediator tetrathiafulvalene (TTF) by means of dialysis membrane. The analytical performance of the biosensor was evaluated when it was used as amperometric detector in three different analytical methodologies: stirred solutions, semiautomatic FIA system and automatic bioanalyzer. The bienzyme biosensor exhibited great analytical performance in terms of sensitivity, selectivity and reproducibility of the measurements and its usefulness was demonstrated by analyzing wine reference materials with certified content of L-malic acid. The attractive analytical and operational characteristics demonstrated by the automatic bioanalyzer make it a promising simple, rapid and field-based tool for routine wine and fruit control. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Self-assembled architectures with segregated donor and acceptor units of a dyad based on a monopyrrolo-annulated TTF-PTM radical.

    Science.gov (United States)

    Souto, Manuel; Solano, Marta V; Jensen, Morten; Bendixen, Dan; Delchiaro, Francesca; Girlando, Alberto; Painelli, Anna; Jeppesen, Jan O; Rovira, Concepció; Ratera, Imma; Veciana, Jaume

    2015-06-08

    An electron donor-acceptor dyad based on a polychlorotriphenylmethyl (PTM) radical subunit linked to a tetrathiafulvalene (TTF) unit through a π-conjugated N-phenyl-pyrrole-vinylene bridge has been synthesized and characterized. The intramolecular electron transfer process and magnetic properties of the radical dyad have been evaluated by cyclic voltammetry, UV/Vis spectroscopy, vibrational spectroscopy, and ESR spectroscopy in solution and in the solid state. The self-assembling abilities of the radical dyad and of its protonated non-radical analogue have been investigated by X-ray crystallographic analysis, which revealed that the radical dyad produced a supramolecular architecture with segregated donor and acceptor units in which the TTF subunits were arranged in 1D herringbone-type stacks. Analysis of the X-ray data at different temperatures suggests that the two inequivalent molecules that form the asymmetric unit of the crystal of the radical dyad evolve into an opposite degree of electronic delocalization as the temperature decreases. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Processing and Performance of Polymeric Transparent Conductive Composites

    Directory of Open Access Journals (Sweden)

    Parul Jain

    2013-01-01

    Full Text Available Recent advances in microelectronic and optoelectronic industries have spurred interest in the development of reticulate doped polymer films containing “metallic” charge transfer complexes. In this study, such reticulate doped polymer films were prepared by exposing solid solutions of bis(ethylenedioxy tetrathiafulvalene (BEDO-TTF in polycarbonate (PC to iodine, forming conductive charge transfer complexes. The resulting films exhibited room temperature conductivities ranging from 6.33 to  S    cm−1. The colored iodine complexes in the film were reduced by cyclic voltammetry yielding conductive, colorless, transparent films. We were intrigued to examine the dielectric properties of BEDO-TTF in solid solution in PC prior to formation of the charge transfer complex as no such studies appear in the literature. Dielectric analysis (DEA was used to probe relaxations in neat PC and BEDO-TTF/PC. BEDO-TTF plasticized the PC and decreased the glass transition temperature. Two secondary relaxations appeared in PC films, whereas the transitions merged in the BEDO-TTF/PC film. DEA also evidenced conductivity relaxations above 180°C which are characterized via electric modulus formalism and revealed that BEDO-TTF increased AC conductivity in PC.

  8. Simultaneous determination of cadaverine and putrescine using a disposable monoamine oxidase based biosensor.

    Science.gov (United States)

    Henao-Escobar, Wilder; Domínguez-Renedo, Olga; Asunción Alonso-Lomillo, M; Julia Arcos-Martínez, M

    2013-12-15

    The selective and simultaneous amperometric determination of putrescine (Put) and cadaverine (Cad) has been carried out using a novel design of screen-printed carbon electrode (SPCE) with two working electrodes connected in array mode. A mixture of 3% of tetrathiafulvalene (TTF), as mediator, and carbon ink was used for the construction of the screen-printed working electrode. The employment of different amounts of monoamine oxidase (MAO) enzyme on these modified TTF/SPCEs and the use of gold nanoparticles (AuNPs) allowed performing the simultaneous determination of both analytes. The amperometric detection has been performed by measuring the oxidation current of the mediator at a potential of+250 mV vs. screen-printed Ag/AgCl reference electrode. A linear response in the Cad concentration range from 19.6 till 107.1 µM and from 9.9 till 74.1 μM for Put was obtained at the MAO/AuNPs/TTF/SPCE biosensor. This device showed a capability of detection of 9.9 and 19.9±0.9 µM (n=4 α=β=0.05) and a precision of 4.9% and 10.3% in terms of relative standard deviation for Put and Cad, respectively. The developed biosensor was successfully applied to the simultaneous determination of Put and Cad in octopus samples. © 2013 Elsevier B.V. All rights reserved.

  9. Forces in EDO-TTF: Theoretical study of isotope and charge effects on vibronic coupling

    Science.gov (United States)

    Tokunaga, Ken

    Isotope and charge effects on vibronic coupling constant (V) and energy gradient (g) of ethylenedioxy-tetrathiafulvalen (EDO-TTF) upon the electron injection into cation and electron removal from neutral molecule are investigated. It is found that normal modes which include C = C stretching motion generally have large V and g. For electron removal, three normal modes (v460, v470, and v480) have large Vi+ and gi+, and deuteration results in decrease of V46+ and increase of V47+. For electron injection, five normal modes (ν+42, ν+44, ν+45, ν+47, and ν+48) have large vi0 and gi0 deuteration results in increase of V045 and V048 and decrease of V047. From the analysis of vibronic coupling constants using vibronic coupling density (VCD), regional vibronic coupling constant (RVCC), and atomic vibronic coupling constant (AVCC), it is revealed that the change in normal mode vectors (d) due to the deuteration and electron removal (or injection) leads to the change in V.

  10. Donor-Acceptor Properties of a Single-Molecule Altered by On-Surface Complex Formation.

    Science.gov (United States)

    Meier, Tobias; Pawlak, Rémy; Kawai, Shigeki; Geng, Yan; Liu, Xunshan; Decurtins, Silvio; Hapala, Prokop; Baratoff, Alexis; Liu, Shi-Xia; Jelínek, Pavel; Meyer, Ernst; Glatzel, Thilo

    2017-08-22

    Electron donor-acceptor molecules are of outstanding interest in molecular electronics and organic solar cells for their intramolecular charge transfer controlled via electrical or optical excitation. The preservation of their electronic character in the ground state upon adsorption on a surface is cardinal for their implementation in such single-molecule devices. Here, we investigate by atomic force microscopy and scanning tunneling microscopy a prototypical system consisting of a π-conjugated tetrathiafulvalene-fused dipyridophenazine molecule adsorbed on thin NaCl films on Cu(111). Depending on the adsorption site, the molecule is found either in a nearly undisturbed free state or in a bound state. In the latter case, the molecule adopts a specific adsorption site, leading to the formation of a chelate complex with a single Na(+) alkali cation pulled out from the insulating film. Although expected to be electronically decoupled, the charge distribution of the complex is drastically modified, leading to the loss of the intrinsic donor-acceptor character. The chelate complex formation is reversible with respect to lateral manipulations, enabling tunable donor-acceptor molecular switches activated by on-surface coordination.

  11. Interface molecular dipoles on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez-Torrente, Isabel; Franke, Katharina Jennifer; Henningsen, Nils; Pascual, Jose [Institut fuer Experimentalphysik, Freie Universitaet Berlin (Germany); Monturet, Sergio; Lorente, Nicolas [Universite Paul Sabatier, Toulouse (France)

    2007-07-01

    Association of molecules with donor and acceptor character forms the so called molecular charge transfer complexes. Tetrathiafulvalene 7,7,8,8-tetracyanoquinodimethane (TTF-TCNQ) is a well-known example of a compound with a metal conducting behaviour governed by charge transfer interactions between the TTF (donor) and the TCNQ (acceptor). Here we report on the submonolayer growth of TTF on a Au(111) surface studied by Low Temperature Scanning Tunneling Microscopy. We find that TTF lies tilted on the surface and two S atoms dominate the adsorption. As a function of coverage we resolve several phases of the growth with different dimensionalities. In combination with DFT calculations we show that the growth is mediated by the balance between a repulsive and an attractive interaction. The repulsive force is associated to the creation of a dipole between TTF and the metallic surface while the attractive interaction is related to the formation of intermolecular H-bonds. At low coverage, molecules show primarily repulsion and they adsorb as monomers. As the coverage increases the attractive interaction gains importance and the molecules self-assemble in one and two dimensional structures.

  12. Interface characterization of TTF-TCNQ on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez-Torrente, Isabel; Franke, Katharina J.; Henningsen, Nils; Pascual, Jose [Institut fuer Experimentalphysik, Freie Universitaet Berlin (Germany); Monturet, Sergio; Lorente, Nicolas [Universite Paul Sabatier, Toulouse (France); Fraxedas, Jordi [ICMAB, Campus UAB, Bellatera (Spain)

    2007-07-01

    Molecular charge transfer (CT) complexes are defined as the association of donor and acceptor molecules. The self-assembling properties of molecules open the possibility of building different donor-acceptor stacking structures which rule the electronic functionality of the compound. Tetrathiafulvalene 7,7,8,8-tetracyanoquinodimethane (TTF-TCNQ) is an example of a CT complex which shows a metal conducting behaviour. The stacking of TTF and TCNQ forms in bulk one-dimensional partially occupied energy bands that gives rise to the metallicity. By means of Low Temperature Scanning Tunneling Microscopy/Spectroscopy we have characterised for the first time the mixed growth of TTF and TCNQ on a metallic surface in submonolayer and monolayer regimes. The self-assembled growth is governed by donor-acceptor recognition. In particular a one dimensional phase with alternating lines of TTF and TCNQ is formed and can be considered as the precursor stage for the bulk structure. By Scanning Tunneling Spectroscopy we associate electronic resonances with the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) of TTF and TCNQ and the self-assembled TTF-TCNQ.

  13. Hydrogen bond-promoted metallic state in a purely organic single-component conductor under pressure.

    Science.gov (United States)

    Isono, Takayuki; Kamo, Hiromichi; Ueda, Akira; Takahashi, Kazuyuki; Nakao, Akiko; Kumai, Reiji; Nakao, Hironori; Kobayashi, Kensuke; Murakami, Youichi; Mori, Hatsumi

    2013-01-01

    Purely organic materials are generally insulating. Some charge-carrier generation, however, can provide them with electrical conductivity. In multi-component organic systems, carrier generation by intermolecular charge transfer has given many molecular metals. By contrast, in purely organic single-component systems, metallic states have rarely been realized although some neutral-radical semiconductors have been reported. Here we uncover a new type of purely organic single-component molecular conductor by utilizing strong hydrogen-bonding interactions between tetrathiafulvalene-based electron-donor molecules. These conductors are composed of highly symmetric molecular units constructed by the strong intra-unit hydrogen bond. Moreover, we demonstrate that, in this system, charge carriers are produced by the partial oxidation of the donor molecules and delocalized through the formation of the symmetric intra-unit hydrogen bonds. As a result, our conductors show the highest room-temperature electrical conductivity and the metallic state under the lowest physical pressure among the purely organic single-component systems, to our knowledge.

  14. Shape-controlled synthesis of hybrid nanomaterials via three-dimensional hydrodynamic focusing.

    Science.gov (United States)

    Lu, Mengqian; Yang, Shikuan; Ho, Yi-Ping; Grigsby, Christopher L; Leong, Kam W; Huang, Tony Jun

    2014-10-28

    Shape-controlled synthesis of nanomaterials through a simple, continuous, and low-cost method is essential to nanomaterials research toward practical applications. Hydrodynamic focusing, with its advantages of simplicity, low-cost, and precise control over reaction conditions, has been used for nanomaterial synthesis. While most studies have focused on improving the uniformity and size control, few have addressed the potential of tuning the shape of the synthesized nanomaterials. Here we demonstrate a facile method to synthesize hybrid materials by three-dimensional hydrodynamic focusing (3D-HF). While keeping the flow rates of the reagents constant and changing only the flow rate of the buffer solution, the molar ratio of two reactants (i.e., tetrathiafulvalene (TTF) and HAuCl4) within the reaction zone varies. The synthesized TTF-Au hybrid materials possess very different and predictable morphologies. The reaction conditions at different buffer flow rates are studied through computational simulation, and the formation mechanisms of different structures are discussed. This simple one-step method to achieve continuous shape-tunable synthesis highlights the potential of 3D-HF in nanomaterials research.

  15. Crystal structure of ethylenedioxytetrathiafulvalene-4,5-bis(thiolbenzoic acid 0.25-hydrate

    Directory of Open Access Journals (Sweden)

    Yuanyuan Zhang

    2017-09-01

    Full Text Available In the title compound (systematic name: 4,4′-{[2-(5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dioxin-2-ylidene-1,3-dithiole-4,5-diyl]bis(sulfanediyl}dibenzoic acid 0.25-hydrate, C22H14O6S6·0.25H2O, the tetrathiafulvalene (TTF core adopts a boat conformation, where the central S2C=CS2 plane makes dihedral angles of 31.34 (4 and 26.83 (6°, respectively, with the peripheral S2C=CS2 and S2C2O2 planes. In the crystal, the benzoic acid molecules are linked via O—H...O hydrogen bonds, forming inversion dimers with R22(8 motifs. The dimers are linked through weak C—H...O hydrogen bonds into a chain structure along [-101]. The chains stack along the a axis through S...S and S...C short contacts, forming layers parallel to the ac plane.

  16. Validation of intermolecular transfer integral and bandwidth calculations for organic molecular materials.

    Science.gov (United States)

    Huang, Jingsong; Kertesz, Miklos

    2005-06-15

    We present an interpretation of the intermolecular transfer integral that is independent from the origin of the energy scale allowing convergence studies of this important parameter of organic molecular materials. We present extensive numerical studies by using an ethylene pi dimer to investigate the dependence of transfer integrals on the level of theory and intermolecular packing. Transfer integrals obtained from semiempirical calculations differ substantially from one another and from ab initio results. The ab initio results are consistent across all the levels used including Hartree-Fock, outer valence Green's function, and various forms of density functional theory (DFT). Validation of transfer integrals and bandwidths is performed by comparing the calculated values with the experimental values of tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ), bis[1,2,5]thiadiazolo-p-quinobis(1,3-dithiole), (BTQBT) K-TCNQ, and hexagonal graphite. DFT in one of its presently popular forms, such as Perdew-Wang functionals (PW91), in combination with sufficient basis sets provides reliable transfer integrals, and therefore can serve as a basis for energy band calculations for soft organic materials with van der Waals gaps.

  17. Structural Diversity in the Complexes of Trimeric Perfluoro- o -phenylene Mercury with Tetrathia- and Tetramethyltetraselenafulvalene

    Energy Technology Data Exchange (ETDEWEB)

    Castañeda, Raúl [New Mexico Highlands Univ., Las Vegas, NV (United States); Yakovenko, Andrey A. [Argonne National Lab. (ANL), Argonne, IL (United States); Draguta, Sergiu [New Mexico Highlands Univ., Las Vegas, NV (United States); Fonari, Marina S. [New Mexico Highlands Univ., Las Vegas, NV (United States); Academy of Sciences of Moldova, Chisinau (Moldova); Antipin, Mikhail Yu. [New Mexico Highlands Univ., Las Vegas, NV (United States); Russian Academy of Sciences (RAS), Moscow (Russian Federation); Timofeeva, Tatiana V. [New Mexico Highlands Univ., Las Vegas, NV (United States); ITMO Univ., St. Petersburg (Russia)

    2015-03-04

    Five potential charge transfer complexes of trimeric perfluoro-o-phenylene mercury (I) with tetrathiafulvalene (TTF) and tetramethyltetraselenefulvalene (TMTSF) were grown from different solvent mixtures. The adducts (I)2·TTF (1) and I·TTF (2) were grown by slow evaporation from the 1:1 mixture of dichloromethane (CH2Cl2, DCM) and carbon disulfide (CS2). Use of the different 1:1 solvent mixtures of dichloromethane (CH2Cl2, DCM) and dichloroethane (C2H4Cl2, DCE) has led to the crystalline adducts I·TTF (3) and I·TTF·DCE (4). Adduct I.TMTSF (5) was grown by the interface crystallization on the border of two immiscible layers, ethyl acetate, and carbon disulfide. The cocrystals differ by the donor–acceptor ratio, molecular packing, and the solvent inclusion. The components in 1–5 form mixed donor–acceptor stacks. The stacks are stabilized by Hg···S and Hg···C short contacts, while the lateral interactions between stacks include F···F, CH···F, and S/Se···F short contacts.

  18. 3-D coordination polymers based on the tetrathiafulvalenetetracarboxylate (TTF-TC) derivative: synthesis, characterization, and oxidation issues.

    Science.gov (United States)

    Nguyen, Thi Le Anh; Demir-Cakan, Rezan; Devic, Thomas; Morcrette, Mathieu; Ahnfeldt, Tim; Auban-Senzier, Pascale; Stock, Norbert; Goncalves, Anne-Marie; Filinchuk, Yaroslav; Tarascon, Jean-Marie; Férey, Gérard

    2010-08-02

    The reactivity of the redox-active tetracarboxylic acid derived from the tetrathiafulvalene (TTF-TC)H(4) with alkaline cations (K, Rb, Cs) is reported. The exploration of various experimental parameters (temperature, pH) led to the formation of four crystalline three-dimensional coordination polymers formulated M(2)(TTF-TC)H(2) (M = K, Rb, Cs), denoted MIL-132(K), MIL-133(isostructural K, Rb), and MIL-134(Cs). Thermogravimetric analysis and thermodiffraction show that all of the solids are thermally stable up to 150-200 degrees C in the air. In order to exploit the possibility of oxidation of the organic linker in TTF-based compounds, they were employed as positive electrodes in a classical lithium cell. A highly reversible cyclability was achieved at high current density (10 C) with a reasonable performance (approximately 50 mAh g(-1)). Finally, combined electro-(sub)hydrothermal synthesis was used to prepare a fifth 3-D coordination polymer formulated K(TTF-TC)H(2) (denoted MIL-135(K)), this time not based on the neutral TTF-TC linker but its radical, oxidized form TTF-TC(+*). This solid is less thermally stable than its neutral counterparts but exhibits a semiconducting behavior, with a conductivity at room temperature of about 1 mS cm(-1).

  19. Preparation of hybrid devices containing nylon/M(II)Pc-TTF (M=Cu, Zn) films with potential optical and electrical applications

    Science.gov (United States)

    Sánchez-Vergara, María Elena; López-Romero, Diana Monserrat; Vidal-García, Pablo; Jiménez-Jarquín, Christian; Hernandez-García, Aline; Jiménez-Sandoval, Omar

    2017-05-01

    Hybrid devices consisting of metallophthalocyanines, MPcs (M=Zn, Cu), doped with a Tetrathiafulvalene (TTF) derivative and dispersed in nylon 11 have been prepared by using a thermal evaporation technique. The effects of thermal relaxation on the structure and morphology of the samples were studied by FT-IR spectroscopy, SEM and X-ray diffraction. The thermal relaxation in nylon 11 produced a crystalline arrangement in the α- and β-form MPc molecules. Changes in conductivity of the devices suggest the formation of alternative paths for carrier conduction. It was found that the temperature-dependent electric current in Zn devices showed a semiconductor behavior. Finally, the optical direct and indirect band gap of these hybrid devices was evaluated from optical absorption measurements. The band gap values were found to decrease from 3.7 to 1.38 eV (for the ZnPc device), and from 1.9 to 1.1 eV (for the CuPc device), with the addition of TTF in the polymeric matrix. [Figure not available: see fulltext.

  20. Complexation and Electronic Communication between Corannulene-Based Buckybowls and a Curved Truxene-TTF Donor.

    Science.gov (United States)

    Gallego, María; Calbo, Joaquín; Krick Calderon, Rafael M; Pla, Paula; Hsieh, Ya-Chu; Pérez, Emilio M; Wu, Yao-Ting; Ortí, Enrique; Guldi, Dirk M; Martín, Nazario

    2017-03-13

    The association behavior of an electron-donating, bowl-shaped, truxene-based tetrathiafulvalene (truxTTF) with two corannulene-based fullerene fragments, C32 H12 and C38 H14 , is investigated in several solvents. Formation of 1:1 complexes is followed by absorption titrations and complemented by density functional theory (DFT) calculations. The binding constants are in the range log Ka =2.9-3.5. DFT calculations reveal that the most stable arrangement is the conformation in which the 1,3-dithiole ring of truxTTF is placed inside the concave cavity of the corannulene derivative. This arrangement is confirmed experimentally by NMR measurements, and implies that a combination of π-π and CH-π interactions is the driving force for association. Time-dependent DFT calculations reproduce the experimental UV/Vis titrations and provide a detailed understanding of the spectral changes observed. Femtosecond transient absorption studies reveal the processes occurring after photoexcitation of either C32 H12 or C38 H14 and their supramolecular associates with truxTTF. In the case of truxTTF⋅C38 H14 , photoexcitation yields the charge-separated state truxTTF(.+) ⋅C38 H14(.-) with a lifetime of approximately 160 ps. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Enantiopure and racemic radical-cation salts of bis(2'-hydroxylpropylthio)(ethylenedithio)TTF with polyiodide anions.

    Science.gov (United States)

    Martin, Lee; Wallis, John D; Guziak, Milena; Maksymiw, Peter; Konalian-Kempf, Florence; Christian, Anthony; Nakatsuji, Shin'ichi; Yamada, Jun'ichi; Akutsu, Hiroki

    2017-03-27

    The chiral TTF-based donor molecule bis(2'-hydroxylpropylthio)(ethylenedithio)tetrathiafulvalene (BHPT-EDT-TTF) has produced enantiopure R,R and S,S radical-cation salts with polyiodide anions I3- and I82-. Enantiomorphic 6 : 6 donor : I3 phases grown from either the R,R or S,S donor are semiconducting with similar activation energies of 0.24-0.30 eV and 0.22-0.23 eV, respectively, and contain three unique face-to-face donor pairs whose relative orientation is determined by side chain conformations and hydrogen bonding. Racemic material under the same conditions gave an insulating centrosymmetric phase with R,R and S,S donor cations in a face-to-face pair partnered with an octaiodide dianion, and with a ca. 3 : 1 disorder between the enantiomers. Enantiopure BHPT-EDT-TTF yielded two further insulating crystalline phases of composition 2 : 2 with triiodide and 2 : 1 with octaiodide.

  2. Disposable magnetic DNA sensors for the determination at the attomolar level of a specific enterobacteriaceae family gene.

    Science.gov (United States)

    Loaiza, Oscar A; Campuzano, Susana; Pedrero, María; Pividori, M Isabel; García, Pedro; Pingarrón, José M

    2008-11-01

    Disposable magnetic DNA sensors using an enzyme-amplified strategy for the specific detection of a gene related to the Enterobacteriaceae bacterial family, based on the coupling of streptavidin-peroxidase to biotinylated lacZ gene target sequences, has been developed. A biotinylated 25-mer capture probe was attached to streptavidin-modified magnetic beads and hybridization with the biotinylated target was allowed to proceed. Then, a streptavidin-peroxidase polymer was attached to the biotinylated target, and the resulting modified magnetic beads were captured by a magnetic field on the surface of tetrathiafulvalene (TTF) modified gold screen-printed electrodes (Au/SPEs). The amperometric response obtained at -0.15 V after the addition of hydrogen peroxide was used to detect the hybridization process. In order to improve the sensitivity of the determination and reduce the assay time, different variables of the assay protocol were optimized. A low detection limit (5.7 fmol) with good stability (RSD = 7.1%, n = 10) was obtained. The DNA nonspecific adsorption at the magnetic beads was negligible, the obtained results thus demonstrating the possibility to detect the hybridization event with great specificity and sensitivity. The developed method was used for the analysis of Escherichia coli DNA fragments (326 bases) in polymerase chain reaction (PCR) amplicons extracted from a cell culture. As low as 2.5 aM asymmetric PCR product could be detected with the developed methodology.

  3. A QCM study of ORR-OER and an in situ study of a redox mediator in DMSO for Li-O2 batteries.

    Science.gov (United States)

    Schaltin, Stijn; Vanhoutte, Gijs; Wu, Minxian; Bardé, Fanny; Fransaer, Jan

    2015-05-21

    The oxygen reduction reaction and oxygen evolution reaction (ORR-OER) in DMSO were investigated by cyclic voltammetry and potentiostatic methods. A quartz crystal microbalance (QCM) was used to detect which products are formed during reduction and to evaluate the reversibility of the reactions. The studied parameters include the scan rate and the applied cathodic potential. We confirm by the QCM that LiO2 is soluble: this conclusion comes from the time delay we observed between the deposition of the expected mass (based on Faraday's law) and the measured mass. Ambiguity in reported literature values for the slope of the deposited mass per electron M/z is due to the negligence in considering this time delay. The average M/z value versus cathodic charge indicates that soluble LiO2 is the first product of the ORR which reacts further to form Li2O2, either via a disproportionation reaction or via further electrochemical reduction of LiO2. For strong negative potentials and thus large depths of discharge, Li2O is the main discharge product. The reaction pathways hence strongly depend on the experimental conditions applied; especially the reduction potential. The redox mediator tetrathiafulvalene (TTF) was investigated and its influence on reversibility was confirmed by cycling at moderate depths of discharge, where Li2O2 is the main discharge product.

  4. Electronic and structural effects on the nonlinear optical behavior in push-pull TTF/tricarbonyl chromiun arene complexes.

    Science.gov (United States)

    Insuasty, Braulio; Atienza, Carmen; Seoane, Carlos; Martín, Nazario; Garín, Javier; Orduna, Jesús; Alcalá, Rafael; Villacampa, Belén

    2004-10-15

    A novel D-pi-A system in which tetrathiafulvalene (TTF) and pi-extended TTFs as strong electron donors are covalently connected to a tricarbonyl (eta(6)-arene)chromium complex as the acceptor moiety through a systematically increased conjugated bridge of vinylene units (12a-c, 16a-c) have been synthesized by Wittig-Horner olefination reaction. The electronic spectra as well as the electrochemical data reveal a different behavior of TTF derivatives (12a-c) and of exTTF derivatives (16a-c). Cyclic voltammetry shows the influence of the tricarbonylchromium arene on the oxidation potentials in compounds 12a-c, and no remarkable effect is observed for exTTFs (16a-c). The nonlinear optical properties of 12a-c and 16a-c have been calculated by using the ab initio CPHF/6-31G//B3P86/6-31G model, and the time-dependent density functional theory (TD-DFT) method has been used for the calculation of the electronic transitions. The calculations reveal that an intraligand charge-transfer transition (ILCT) and the metal to ligand charge-transfer transition (MLCT) are responsible for the nonlinear response. In addition, the large angles formed by the ground-state dipole moment and the vectorial hyperpolarizability are responsible for the mubeta values determined experimentally by the EFISH technique.

  5. Quantum vortex melting and phase diagram in the layered organic superconductor κ -(BEDT-TTF)2Cu(NCS ) 2

    Science.gov (United States)

    Uji, S.; Fujii, Y.; Sugiura, S.; Terashima, T.; Isono, T.; Yamada, J.

    2018-01-01

    Resistance and magnetic torque measurements have been performed to investigate vortex phases for a layered organic superconductor κ -(BEDT-TTF) 2Cu (NCS) 2 [BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene], which is modeled as stacks of Josephson junctions. At 25 mK, the out-of-plane resistivity increases at 0.6 T, has a step feature up to 4 T, and then increases again, whereas the in-plane resistivity monotonically increases above 4 T. The results show that both pancake vortices (PVs) and Josephson vortices (JVs) are in solid phases for μ0H 4 T, both PVs and JVs are in liquid phases. These melting transitions are predominantly induced by quantum fluctuations (not by thermal fluctuations). In the magnetic torque curves, the irreversibility transition is clearly observed, roughly corresponding to the melting transition of the PVs but no anomaly is found at the JV melting transition. The detailed vortex phase diagram is determined in a wide temperature region.

  6. Charge Density Analysis and Transport Properties of TTF Based Molecular Nanowires: A DFT Approach

    Directory of Open Access Journals (Sweden)

    Karuppannan Selvaraju

    2015-01-01

    Full Text Available The present study has been performed to understand the charge density distribution and the electrical characteristics of Au and thiol substituted tetrathiafulvalene (TTF based molecular nanowire. A quantum chemical calculation has been carried out using DFT method (B3LYP with the LANL2DZ basis set under various applied electric fields (EFs. The bond topological analysis characterizes the terminal Au–S and S–C bonds as well as all the bonds of central TTF unit of the molecule. The variation of electron density and Laplacian of electron density at the bond critical point of bonds for zero and different applied fields reveal the electron density distribution of the molecule. The molecular conformation, the variation of atomic charges and energy density distribution of the molecule have been analyzed for the various levels of applied EFs. The HOMO-LUMO gap calculated from quantum chemical calculations has been compared with the value calculated from the density of states. The variation of dipole moment due to the polarization effect and the I-V characteristics of the molecule for the various applied EFs have been well discussed.

  7. Mott transition by an impulsive dielectric breakdown

    Science.gov (United States)

    Yamakawa, H.; Miyamoto, T.; Morimoto, T.; Terashige, T.; Yada, H.; Kida, N.; Suda, M.; Yamamoto, H. M.; Kato, R.; Miyagawa, K.; Kanoda, K.; Okamoto, H.

    2017-11-01

    The transition of a Mott insulator to metal, the Mott transition, can occur via carrier doping by elemental substitution, and by photoirradiation, as observed in transition-metal compounds and in organic materials. Here, we show that the application of a strong electric field can induce a Mott transition by a new pathway, namely through impulsive dielectric breakdown. Irradiation of a terahertz electric-field pulse on an ET-based compound, κ-(ET) 2Cu[N(CN) 2]Br (ET:bis(ethylenedithio)tetrathiafulvalene), collapses the original Mott gap of ~30 meV with a ~0.1 ps time constant after doublon-holon pair productions by quantum tunnelling processes, as indicated by the nonlinear increase of Drude-like low-energy spectral weights. Additionally, we demonstrate metallization using this method is faster than that by a femtosecond laser-pulse irradiation and that the transition dynamics are more electronic and coherent. Thus, strong terahertz-pulse irradiation is an effective approach to achieve a purely electronic Mott transition, enhancing the understanding of its quantum nature.

  8. Dielectric response of modified Hubbard models with neutral-ionic and Peierls transitions.

    Science.gov (United States)

    Soos, Zoltan G; Bewick, Sharon A; Peri, Andrea; Painelli, Anna

    2004-04-08

    The dipole P(F) of systems with periodic boundary conditions in a static electric field F is applied to one-dimensional Peierls-Hubbard models for organic charge-transfer (CT) salts. Exact results for P(F) are obtained for finite systems of N=14 and 16 sites that are almost converged to infinite chains in deformable lattices subject to a Peierls transition. The electronic polarizability per site, alpha(el)=(partial differential P/partial differential F)0, of rigid stacks with alternating transfer integrals t(1+/-delta) diverges at the neutral-ionic transition for delta=0 but remains finite for delta>0 in dimerized chains. The Peierls or dimerization mode couples to charge fluctuations along the stack and results in large vibrational contributions alpha(vib) that are related to partial differential P/ partial differential delta and that peak sharply at the Peierls transition. The extension of P(F) to correlated electronic states yields the dielectric response kappa of models with neutral-ionic or Peierls transitions, where kappa peaks >100 are found with parameters used previously for variable ionicity rho and vibrational spectra of CT salts. The calculated kappa accounts for the dielectric response of CT salts based on substituted TTF's (tetrathiafulvalene) and substituted CA's (chloranil). The role of lattice stiffness appears clearly in models: soft systems have a Peierls instability at small rho and continuous crossover to large rho, while stiff stacks such as TTF-CA have a first-order transition with discontinuous rho that is both a neutral-ionic and Peierls transition. The transitions are associated with tuning the electronic ground state of insulators via temperature or pressure in experiments, or via model parameters in calculations. (c) 2004 American Institute of Physics

  9. Amperometric biosensors for glucose, lactate, and glycolate based on oxidases and redox-modified siloxane polymers

    Energy Technology Data Exchange (ETDEWEB)

    Hale, P.D.; Inagaki, Toru; Lee, Hung Sui; Skotheim, T.A.; Karan, Hiroko I.; Okamoto, Yoshi (Brookhaven National Lab., Upton, NY (USA); Medgar Evers Coll., Brooklyn, NY (USA). Div. of Natural Science and Mathematics; Polytechnic Univ., Brooklyn, NY (USA). Dept. of Chemistry)

    1989-01-01

    Amperometric biosensors based on flavin-containing oxidases undergo several steps which produce a measurable current that is related to the concentration of substrate. In the initial step, the substrate converts the oxidized flavin adenine dinucleotide (FAD) or flavin mononucleotide (FMN) into the reduced form (FADH{sub 2} or FMNH{sub 2}). Because these cofactors are located well within the enzyme molecule, direct electron transfer to the surface of a conventional electrode does not occur to a measurable degree. A common method of facilitating this electron transfer is to introduce oxygen into the system because it is the natural acceptor for the oxidases; the oxygen is reduced by the FADH{sub 2} or FMNH{sub 2} to hydrogen peroxide, which can then be detected electrochemically. The major drawback to this approach is the fact that oxidation of hydrogen peroxide requires a large overpotential, thus making these sensors susceptible to interference from electroactive species. To lower the necessary applied potential, several non-physiological redox couples have been employed to shuttle electrons between the flavin moieties and the electrode. For example, sensors based on the ferrocene/ferricinium redox couple and on electrodes consisting of conducting salts such as TTF-TCNQ (tetrathiafulvalene-tetracyanoquinodimethane) have previously been reported. Electron relays have also been attached directly to the enzyme molecule to facilitate electron transfer. More recently, these studies have been extended to include systems where the mediating redox species are covalently attached to polymers such as poly(pyrrole), poly(vinylpyridine), and poly(siloxane). The present paper describes the development of amperometric biosensors based on flavin-containing enzymes and this latter family of polymeric mediators. 9 refs., 5 figs.

  10. Advances in the synthesis of functionalised pyrrolotetrathiafulvalenes

    Directory of Open Access Journals (Sweden)

    Luke J. O’Driscoll

    2015-07-01

    Full Text Available The electron-donor and unique redox properties of the tetrathiafulvalene (TTF, 1 moiety have led to diverse applications in many areas of chemistry. Monopyrrolotetrathiafulvalenes (MPTTFs, 4 and bispyrrolotetrathiafulvalenes (BPTTFs, 5 are useful structural motifs and have found widespread use in fields such as supramolecular chemistry and molecular electronics. Protocols enabling the synthesis of functionalised MPTTFs and BPTTFs are therefore of broad interest. Herein, we present the synthesis of a range of functionalised MPTTF and BPTTF species. Firstly, the large-scale preparation of the precursor species N-tosyl-(1,3-dithiolo[4,5-c]pyrrole-2-one (6 is described, as well as the synthesis of the analogue N-tosyl-4,6-dimethyl-(1,3-dithiolo[4,5-c]pyrrole-2-one (7. Thereafter, we show how 6 and 7 can be used to prepare BPTTFs using homocoupling reactions and functionalised MPTTFs using cross-coupling reactions with a variety of 1,3-dithiole-2-thiones (19. Subsequently, the incorporation of more complex functionality is discussed. We show how the 2-cyanoethyl protecting group can be used to afford MPTTFs functionalised with thioethers, exemplified by a series of ethylene glycol derivatives. Additionally, the merits of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU as an alternative to the most common deprotecting agent, CsOH·H2O are discussed. Finally, we show how a copper-mediated Ullman-type reaction can be applied to the N-arylation of MPTTFs and BPTTFs using a variety of aryl halides.

  11. Structure-Packing-Property Correlation of Self-Sorted vs. Interdigitated Assembly in TTF.TCNQ Based Charge-Transport Materials.

    Science.gov (United States)

    Niyas, M A; Ramakrishnan, Remya; Vijay, Vishnu; Hariharan, Mahesh

    2018-01-03

    Among the various donor-acceptor (D-A) charge transfer cocrystals investigated in the past few decades, tetrathiafulvalene-tetracyanoquinodimethane (F.Q, popularly known as TTF.TCNQ) based cocrystals have fascinated materials chemists owing to its packing and exceptional properties. Here, crystallographic information files of eighteen F.Q based cocrystals were extracted from Cambridge Structural Database and classified into Class 1 (D on D and A on A segregated stacks; F.Q, F1.Q - F6.Q and F.Q1), Class 2 (-A-D-A-D-A-D- mixed stacks; F6a.Q - F11.Q and F.Q2) and Class 3 (-A-D-A-A-D-A-; Class 3a (F12.Q and F13.Q) and -D-D-A-A-D-D-; Class 3b (F14.Q)) systems based on their packing modes. PIXEL calculations revealed that the Q on Q dimer is the energetically most favored dimer in F.Q, the substituents on F capable of forming hydrogen bonding, C...S and other weak intermolecular interactions resulted in the greater stability of F on F dimer for F1.Q - F6.Q (except F2.Q). Band structure of F.Q and F6.Q with high interaction of electronic orbitals between D on D and A on A in segregated stacks were found to be metal-like (band gap, Eg = 0.003 eV) and metallic (overlapping bands in the Fermi level) respectively while the polymorph of F6.Q belonging to Class 2 (F6a.Q) displayed a semiconductor-type band structure (Eg = 0.053 eV). F12.Q of Class 3a exhibited a metal-like band structure (Eg = 0.001 eV). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Measuring and Reporting Electrical Conductivity in Metal-Organic Frameworks: Cd2(TTFTB) as a Case Study.

    Science.gov (United States)

    Sun, Lei; Park, Sarah S; Sheberla, Dennis; Dincă, Mircea

    2016-11-09

    Electrically conductive metal-organic frameworks (MOFs) are emerging as a subclass of porous materials that can have a transformative effect on electronic and renewable energy devices. Systematic advances in these materials depend critically on the accurate and reproducible characterization of their electrical properties. This is made difficult by the numerous techniques available for electrical measurements and the dependence of metrics on device architecture and numerous external variables. These challenges, common to all types of electronic materials and devices, are especially acute for porous materials, whose high surface area make them even more susceptible to interactions with contaminants in the environment. Here, we use the anisotropic semiconducting framework Cd 2 (TTFTB) (TTFTB 4- = tetrathiafulvalene tetrabenzoate) to benchmark several common methods available for measuring electrical properties in MOFs. We show that factors such as temperature, chemical environment (atmosphere), and illumination conditions affect the quality of the data obtained from these techniques. Consistent results emerge only when these factors are strictly controlled and the morphology and anisotropy of the Cd 2 (TTFTB) single-crystal devices are taken into account. Most importantly, we show that depending on the technique, device construction, and/or the environment, a variance of 1 or even 2 orders of magnitude is not uncommon for even just one material if external factors are not controlled consistently. Differences in conductivity values of even 2 orders of magnitude should therefore be interpreted with caution, especially between different research groups comparing different compounds. These results allow us to propose a reliable protocol for collecting and reporting electrical properties of MOFs, which should help improve the consistency and comparability of reported electrical properties for this important new class of crystalline porous conductors.

  13. Syntheses, structure and properties of vinylogous EDO-TTFs

    Science.gov (United States)

    Shirahata, T.; Morikawa, T.; Miyamoto, H.; Nakano, Y.; Yamochi, H.; Misaki, Y.

    2010-06-01

    We synthesized vinylogous 4,5-ethylenedioxy-tetrathiafulvalenes (EDO-TTFs), 4,5-ethylenedioxy-2,2‧-ethanediylidenebis(1,3-dithiole) (EDO-EBDT), 4,5-dimethyl-4‧,5‧-ethylenedioxy-2,2‧-ethanediylidenebis(1,3-dithiole) (DMEDO-EBDT), 4,5-bis(thiomethyl)-4‧,5‧-ethylenedioxy-2,2‧-ethanediylidenebis(1,3-dithiole) (BTMEDO-EBDT), and 4,5-bis(methoxycarbonyl)-4‧,5‧-ethylenedioxy-2,2‧-ethanediylidenebis(1,3-dithiole) (BMCEDO-EBDT). The cyclic voltammograms of the vinylogous EDO-TTFs show two pairs of single-electron redox waves. The first oxidation potentials (E1) of vinylogous EDO-TTFs are lower than those of the related TTFs, indicating that the electron donating abilities of new donors are stronger than those of the corresponding TTFs. The smaller E2-E1 values of new donors compared with those of the related TTFs suggest a decrease in the on-site Coulombic repulsion in the dication state. X-ray crystal structure analysis of BMCEDO-EBDT reveals that the inter-molecular C-H⋯O type hydrogen bond is constructed between the hydrogen atom and the oxygen atom of the ethylenedioxy group. Single crystalline TCNQ complexes of DMEDO-EBDT and BTMEDO-EBDT have been prepared and their conducting properties and crystal structure have been investigated. The TCNQ complexes of DMEDO-EBDT and BTMEDO-EBDT show low electrical conductivities (σrt<10-6 S cm-1 for (DMEDO-EBDT)(TCNQ)(chlorobenzene) and σrt=2.2×10-3 S cm-1 for (BTMEDO-EBDT)(TCNQ)) due to DDAA-type alternate stacking.

  14. Integrated multienzyme electrochemical biosensors for monitoring malolactic fermentation in wines.

    Science.gov (United States)

    Gamella, M; Campuzano, S; Conzuelo, F; Curiel, J A; Muñoz, R; Reviejo, A J; Pingarrón, José M

    2010-05-15

    Integrated amperometric biosensors for the determination of L-malic and L-lactic acids were developed by coimmobilization of the enzymes L-malate dehydrogenase (MDH) and diaphorase (DP), or L-lactate oxidase (LOX) and horseradish peroxidase (HRP), respectively, together with the redox mediator tetrathiafulvalene (TTF), on a 3-mercaptopropionic acid (MPA) self-assembled monolayer (SAM)-modified gold electrode by using a dialysis membrane. The electrochemical oxidation of TTF at +100mV (vs. Ag/AgCl), and the reduction of TTF(+) at -50mV were used for the monitoring of the enzyme reactions involved in L-malic and L-lactic acid determinations, respectively. Experimental variables concerning the biosensors composition and the detection conditions were optimized for each biosensor. Good relative standard deviation values were obtained in both cases for the measurements carried out with the same biosensor, with no need of cleaning or pretreatment of the bioelectrodes surface, and with different biosensors constructed in the same manner. After 7 days of continuous use, the MDH/DP biosensor still exhibited 90% of the original sensitivity, while the LOX/HRP biosensor yielded a 91% of the original response after 5 days. Calibration graphs for L-malic and L-lactic were obtained with linear ranges of 5.2x10(-7) to 2.0x10(-5) and 4.2x10(-7) to 2.0x10(-5)M, respectively. The calculated detection limits were 5.2x10(-7) and 4.2x10(-7)M, respectively. The biosensors exhibited a high selectivity with no significant interferences. They were applied to monitor malolactic fermentation (MLF) induced by inoculation of Lactobacillus plantarum CECT 748(T) into a synthetic wine. Samples collected during MLF were assayed for L-malic and L-lactic acids, and the results obtained with the biosensors exhibited a very good correlation when plotted against those obtained by using commercial enzymatic kits.

  15. Liquid Redox Electrolytes for Dye-Sensitized Solar Cells

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Ze

    2012-07-01

    This thesis focuses on liquid redox electrolytes in dye-sensitized solar cells (DSCs). A liquid redox electrolyte, as one of the key constituents in DSCs, typically consists of a redox mediator, additives and a solvent. This thesis work concerns all these three aspects of liquid electrolytes, aiming through fundamental insights to enhance the photovoltaic performances of liquid DSCs. Initial attention has been paid to the iodine concentration effects in ionic liquid (IL)-based electrolytes. It has been revealed that the higher iodine concentration required in IL-based electrolytes can be attributed to both triiodide mobility associated with the high viscosity of the IL, and chemical availability of triiodide. The concept of incompletely solvated ionic liquids (ISILs) has been introduced as a new type of electrolyte solvent for DSCs. It has been found that the photovoltaic performance of ISIL-based electrolytes can even rival that of organic solvent-based electrolytes. And most strikingly, ISIL-based electrolytes provide highly stable DSC devices under light-soaking conditions, as a result of the substantially lower vapor pressure of the ISIL system. A significant synergistic effect has been observed when both guanidinium thiocyanate and N-methylbenzimidazole are employed together in an IL-based electrolyte, exhibiting an optimal overall conversion efficiency. Tetrathiafulvalene (TTF) has been investigated as an organic iodine-free redox couple in electrolytes for DSCs. An unexpected worse performance has been observed for the TTF system, albeit it possesses a particularly attractive positive redox potential. An organic, iodine-free thiolate/disulfide system has also been adopted as a redox couple in electrolytes for organic DSCs. An impressive efficiency of 6.0 % has successfully been achieved by using this thiolate/disulfide redox couple in combination with a poly (3, 4-ethylenedioxythiophene) (PEDOT) counter electrode material under full sunlight illumination (AM

  16. Tuning Optoelectronic Properties of Organic Semiconductors Via Donor-Acceptor Cocrystals and Interfacial Composites

    Science.gov (United States)

    Wang, Chen

    Organic donor-acceptor (D-A) interaction has attracted intensive research interest because of the promising applications in electronic devices and renewable energy. Depending on the interaction process, the optoelectronic properties of organic semiconductors may change dramatically. To improve their performance and expand the applications, we have investigated the structure-property relationship in D-A cocrystals and nanofibril composites. These materials provide unique D-A interface structures, thus allowing tunable charge transfer across the interface, which can be modified and controlled by exquisite molecule design and supramolecular assembly. In Chapter 2, we studied the fabrication, conductivity, and chemiresistive sensor performance of tetrathiafulvalene (TTF) - 7,7,8,8-tetracyanoquinodimethane (TCNQ) charge transfer cocrystal microfibers. Compared to TCNQ and TTF, TTF-TCNQ cocrystal has much higher conductivity under ambient conditions, due to the high yield of charge separation, which also induces high polarization at the interface, resulting in different binding intensity towards alkyl and aromatic amines. Based on this investment, we developed a TTF-TCNQ chemiresistive sensor to efficiently discriminate alkyl and aromatic amine vapors. In Chapter 3, we further designed a new series of D-A cocrystals, and studied the coassembly and optical properties. The cocrystal is composed of coronene and perylene diimide at 1:1 molar ratio and belongs to the triclinic system, as confirmed by X-ray analysis. The donor and acceptor molecules perform an alternate pi-pi stacking along the (100) direction, leading to the strong one-dimensional growth tendency of macroscopic cocrystal. Additionally, due to the charge transfer interaction, the cocrystal shows a new and largely red-shifted photoluminescence band, compared to the crystals of the components. In Chapter 4, we alternatively developed a series of donor-acceptor nanofibril composites, in which the donor and

  17. Coupling of electrons to intermolecular phonons in molecular charge transfer dimers: A resonance Raman study

    Science.gov (United States)

    Pedron, D.; Speghini, A.; Mulloni, V.; Bozio, R.

    1995-08-01

    We report resonance Raman scattering (RRS) spectra and Raman excitation profiles (REP) of a system containing π dimers of identical molecular radical ions measured with laser excitation in resonance with the charge transfer (CT) transition. A Peierls-Hubbard (PH) Hamiltonian has been used to model the investigated system and to calculate its optical and RRS properties. Results are reported for two polyoxometallate salts of tetrathiafulvalene (TTF), namely (TTF)2(W6O19) and (TTF)2(Mo6O19) whose structures contain almost isolated (TTF+)2 dimers. The RRS spectra of (TTF)2(W6O19), measured in resonance with the CT absorption band centered at 832 nm, show three phonon modes located at 55, 90, and 116 cm-1 which are strongly resonance enhanced. These modes have been associated to the out-of-phase combinations of the translational motions of the two molecules composing the dimer. Such modes are effective in modulating the intradimer transfer integral, thus providing an efficient mechanism for coupling with the electronic system and for enhancement of the scattering intensity at resonance with the CT transition. The REP for the three strongly coupled modes of (TTF)2(W6O19) have been measured with laser excitation wavelengths ranging from 740 to 930 nm. Quantitative analysis of the REP data has been performed based on a perturbative solution of the PH model to second order in the electron-molecular-vibration (EMV) and electron-intermolecular-phonon (EIP) interactions. The CT absorption profile and the REP's have been calculated using a time correlator technique and the model parameters have been optimized in order to fit the experimental REP data. Infrared vibronic absorptions of (TTF)2(W6O19), originated by the EMV coupling, have been measured and independent information on the electronic parameters of the PH model have been derived. This has made the choice of the fitting parameters used for the REP calculations rather unambiguous and has allowed us to obtain, for the

  18. Self-healing gold mirrors and filters at liquid-liquid interfaces

    Science.gov (United States)

    Smirnov, Evgeny; Peljo, Pekka; Scanlon, Micheál D.; Gumy, Frederic; Girault, Hubert H.

    2016-03-01

    tetrathiafulvalene with neocuproine as the AuNP capping ligand in the nanofilm. These interfacial nanofilms formed with neocuproine and 38 nm mean diameter AuNPs, at monolayer surface coverages and above, were black due to aggregation and broadband absorbance.The optical and morphological properties of lustrous metal self-healing liquid-like nanofilms were systematically studied for different applications (e.g., optical mirrors or filters). These nanofilms were formed by a one-step self-assembly methodology of gold nanoparticles (AuNPs) at immiscible water-oil interfaces, previously reported by our group. We investigated a host of experimental variables and herein report their influence on the optical properties of nanofilms: AuNP mean diameter, interfacial AuNP surface coverage, nature of the organic solvent, and nature of the lipophilic organic molecule that caps the AuNPs in the interfacial nanofilm. To probe the interfacial gold nanofilms we used in situ (UV-vis-NIR spectroscopy and optical microscopy) as well as ex situ (SEM and TEM of interfacial gold nanofilms transferred to silicon substrates) techniques. The interfacial AuNP surface coverage strongly influenced the morphology of the interfacial nanofilms, and in turn their maximum reflectance and absorbance. We observed three distinct morphological regimes; (i) smooth 2D monolayers of ``floating islands'' of AuNPs at low surface coverages, (ii) a mixed 2D/3D regime with the beginnings of 3D nanostructures consisting of small piles of adsorbed AuNPs even under sub-full-monolayer conditions and, finally, (iii) a 3D regime characterised by the 2D full-monolayer being covered in significant piles of adsorbed AuNPs. A maximal value of reflectance reached 58% in comparison with a solid gold mirror, when 38 nm mean diameter AuNPs were used at a water-nitrobenzene interface. Meanwhile, interfacial gold nanofilms prepared with 12 nm mean diameter AuNPs exhibited the highest extinction intensities at ca. 690 nm and absorbance around

  19. Single Molecule Nanoelectrochemistry in Electrical Junctions.

    Science.gov (United States)

    Nichols, Richard J; Higgins, Simon J

    2016-11-15

    gating. This has been referred to as to a "single molecule transistor configuration" with the gate voltage being provided by the controllable potential achieved through the electrochemical double layer. It is shown how the electrolyte medium can control such gating, with ionic liquids providing more efficient gate coupling than aqueous electrolytes. Control of the conductance of viologen molecular wires can also be achieved by encapsulating the viologen redox moiety within a molecular cage, thereby controlling its immediate environment. Molecular conductance can also be gated through multiple redox states. This has been shown for the redox moiety pyrrolo-tetrathiafulvalene, which undergoes single molecule electrochemical transistor gating through three redox states in molecular junctions. Charge transport through this junction follows a two-step hopping mechanism, demonstrating the role of the redox center in electron transfer across the molecular bridge. Recent electrolyte gating studies of rigid, conjugated redox-active metal complexes with tailored terpyridine coordinating ligands and anchors are also presented. These aforementioned studies have all been performed with gold electrode contacts. The Account concludes with recent data showing that it is now possible to study single molecule electrochemical gating with nickel electrodes. This opens up new perspectives for studying interfacial charge transfer with a wide variety of other electrode materials including semiconductor electrodes and also points toward future opportunities for coupling molecular spintronics and nanoelectrochemistry.

  20. Preface

    Science.gov (United States)

    Batail, Patrick

    2004-04-01

    contribute oral presentations - we have decided to keep with as many 20 minutes talks as possible and had to resolve - rather reluctantly to run parallel sessions on Wednesday and Thursday mornings. Yet, in the end, there has been a significant number of solicitations for oral contributions of great interest which were simply impossible to fit in the schedule. We thank all the colleagues who have submitted their exciting work and who have presented their oral and posters contributions during the 23 sessions of the Symposium. Seven sessions were devoted to materials chemistry, of which two sessions dealt more specifically with organic synthesis and two sessions with molecular magnetic materials. The experimental aspects of one- and two-dimensional physics were discussed in two and four sessions, respectively. Aside several theoretical talks interspersed within the former experimental sessions, two sessions were dedicated to theoretical aspects of strongly correlated electron systems in low dimension. One session focused on high magnetic field phenomena and two sessions covered charge ordering phenomena. Finally, upcoming issues related to surface and interface phenomena in molecular conductors were addressed in one session. The current research in chemistry of molecular precursor is dominated by the concepts of multifunctional π systems constructed on tetrathiafulvalene-based redox cores equipped with hydrogen-bond donor-acceptor functionalities or tetrathiafulvalene-based ligands capable of coordinating a metal center. Likewise, in the same spirit, the introduction of chiral functionalities is reported in several contributions. Aside those in the chemistry of stabilized polyacenes and the chemistry of molecular inorganic macrospins species: most of the creative developments continue to involve the TTF platform. In that context, crystal engineering concepts associated with the manipulation of hydrogen bonds and complementary weak intermolecular interactions in competition