WorldWideScience

Sample records for tetrathiafulvalene tetracyanoquinodimethane

  1. Timeresolved investigation of atomic order in tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) monocrystals after excitation with ultrashort light pulses

    International Nuclear Information System (INIS)

    Sager, Christian

    2011-02-01

    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.)

  2. 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.)

  3. 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....

  4. 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...... the donor–acceptor strength of the dyads for numerous applications. The interesting inherent electronic donor properties of TTFs control the overall electrochemical properties of the supramolecular structures, leading to the construction of highly efficient optoelectronic materials, photovoltaic solar cells...

  5. 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.

  6. 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; Sears, John S.; Brédas, Jean-Luc

    2011-01-01

    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.

  7. 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.

  8. 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...

  9. 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...... and by X-ray crystallography....

  10. Fabrication and characterization of tetracyanoquinodimethane/phthalocyanine solar cells

    International Nuclear Information System (INIS)

    Suzuki, Atsushi; Ohtsuki, Takahiro; Oku, Takeo; Akiyama, Tsuyoshi

    2012-01-01

    Highlights: ► Heterojunction solar cells of tetracyanoquinodimethane (TCNQ)/copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc) were fabricated and characterized. ► The light-induced charge separation with charge transfer was investigated by light-induced current density and optical absorption.. ► In both solar cells of TCNQ/CuPc and TCNQ/ZnPc, the TCNQ thin film worked for strong electron-accepting layer. ► These behaviors would be originated in charge transfer of excited electron from CuPc and ZnPc to TCNQ. ► The photovoltaic mechanism was discussed by the experimental results. - Abstract: Fabrication and characterization of heterojunction solar cells of tetracyanoquinodimethane (TCNQ)/copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc) were carried out. The light-induced charge separation with charge transfer was investigated by light-induced current density and optical absorption. In both cases of the TCNQ/CuPc and TCNQ/ZnPc solar cells, the TCNQ thin film worked for strong electron-accepting layer as n-type semiconductor. These behaviors would be originated in charge transfer of excited electron from CuPc and ZnPc to TCNQ. The photovoltaic mechanism was discussed on the basis of the experimental results.

  11. Radioactive iodine absorbing properties of tetrathiafulvalene

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Tomiyasu; Nakamura, Asao (Ajinomoto Co. Inc., Kawasaki, Kanagawa (Japan). Central Research Labs.); Nogawa, Norio; Oohashi, Kunio; Morikawa, Naotake

    1989-05-01

    For the purpose of searching some effective absorbents of gaseous radioactive iodine, 16 substances considered as having an affinity for iodine were investigated with regular iodine and /sup 125/I. In a preliminary survey, only tetrathiafulvalene (TTF) was found to have satisfactory absorbing properties comparable to activated charcoal. A further detailed comparison of the properties between TTF and activated charcoal led us to the conclusion that the former has more preferable properties as absorbent of radioactive iodine than the latter in all points studied. The results are summarized as follows: (1) The absorption of iodine on TTF in atmosphere was about twice as much as that on activated charcoal. Desorption of iodine from saturatedly absorbed iodine on TTF was practically negligible except trace amount of initial desorption, while that on activated charcoal was considerable (3%/50h) even in the air at room temperature. (2) Absorbed amount of iodine on activated charcoal decreased with increasing gaseous iodine concentration, air flow rate, on humidity of flowing-air. On the other hand, those factors scarcely affected that on TTF. Under an air flow rate of 1m/s, activated charcoal absorbs only 80% of iodine, while TTF absorbs more than 99%. (3) In flowing-air saturated with water vapor, iodine absorbed on activated charcoal was gradually liberated although by small amount (0.08%/100h), while that on TTF was much more stable for a long period (0.004%/100h). As a conclusion, TTF is considered to be useful as a quite effective radioactive iodine absorbent, especially in the case where protection from radioactive iodine should be serious, though it is expensive now. (author).

  12. Radioactive iodine absorbing properties of tetrathiafulvalene

    International Nuclear Information System (INIS)

    Ito, Tomiyasu; Nakamura, Asao; Nogawa, Norio; Oohashi, Kunio; Morikawa, Naotake.

    1989-01-01

    For the purpose of searching some effective absorbents of gaseous radioactive iodine, 16 substances considered as having an affinity for iodine were investigated with regular iodine and 125 I. In a preliminary survey, only tetrathiafulvalene (TTF) was found to have satisfactory absorbing properties comparable to activated charcoal. A further detailed comparison of the properties between TTF and activated charcoal led us to the conclusion that the former has more preferable properties as absorbent of radioactive iodine than the latter in all points studied. The results are summarized as follows: (1) The absorption of iodine on TTF in atmosphere was about twice as much as that on activated charcoal. Desorption of iodine from saturatedly absorbed iodine on TTF was practically negligible except trace amount of initial desorption, while that on activated charcoal was considerable (3%/50h) even in the air at room temperature. (2) Absorbed amount of iodine on activated charcoal decreased with increasing gaseous iodine concentration, air flow rate, on humidity of flowing-air. On the other hand, those factors scarcely affected that on TTF. Under an air flow rate of 1m/s, activated charcoal absorbs only 80% of iodine, while TTF absorbs more than 99%. (3) In flowing-air saturated with water vapor, iodine absorbed on activated charcoal was gradually liberated although by small amount (0.08%/100h), while that on TTF was much more stable for a long period (0.004%/100h). As a conclusion, TTF is considered to be useful as a quite effective radioactive iodine absorbent, especially in the case where protection from radioactive iodine should be serious, though it is expensive now. (author)

  13. 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 Ac......O-) to a solution of the sensor. (C) 2012 Elsevier Ltd. All rights reserved....

  14. Self-assembled containers based on extended tetrathiafulvalene.

    Science.gov (United States)

    Bivaud, Sébastien; Goeb, Sébastien; Croué, Vincent; Dron, Paul I; Allain, Magali; Sallé, Marc

    2013-07-10

    Two original self-assembled containers constituted each by six electroactive subunits are described. They are synthesized from a concave tetratopic π-extended tetrathiafulvalene ligand bearing four pyridyl units and cis-M(dppf)(OTf)2 (M = Pd or Pt; dppf = 1,1'-bis(diphenylphosphino)ferrocene; OTf = trifluoromethane-sulfonate) complexes. Both fully characterized assemblies present an oblate spheroidal cavity that can incorporate one perylene molecule.

  15. DFT study on the standard electrode potentials of imidazole, tetrathiafulvalene, and tetrathiafulvalene-imidazole.

    Science.gov (United States)

    Tugsuz, Tugba

    2010-12-30

    Extensive DFT calculations on the standard electrode potentials of imidazole (Im), tetrathiafulvalene (TTF), and 2-, 4-, and 5-TTF-Im were carried out. Geometries and Gibbs free energies of H-bonded dimer, anion, protonated cation, and neutral structures of Im, mono- and dication, and neutral structures of TTF in gas and acetonitrile solvent were computed by using 10 hybrid density functionals (B3LYP, TPSSH, PBEH1PBE, M06, M062X, X3LYP, BMK, B1B95, M05, M052X) combined with the TZVP basis set. CPCM and SMD solvation models were applied to predict the Gibbs free energies of molecules in acetonitrile solvent. Frequency calculations were carried out for all structures, and none of them has been found to exhibit any imaginary frequency. Finally, the BMK hybrid functional was selected for computation of the standard electrode potential of TTF-Im, because it gives the most accurate values in both Im and TTF, differing by 0.05 V from the experimental ones. Moreover, frequencies from the BMK functional are reasonably close to the experimental ones. The standard electrode potentials of 2-, 4-, and 5-TTF-Im predicted for two-electron oxidation are 0.946, 0.870, and 0.839 V in CPCM and 0.927, 0.866, and 0.824 V in SMD. For one-electron oxidation these are 0.491, 0.421, and 0.400 V in CPCM and 0.476, 0.377, and 0.360 V in SMD, respectively.

  16. Formation of an intermolecular charge-transfer compound in UHV codeposited tetramethoxypyrene and tetracyanoquinodimethane

    DEFF Research Database (Denmark)

    Medjanik, K.; Perkert, S.; Naghavi, S.

    2010-01-01

    Ultrahigh vacuum (UHV)-deposited films of the mixed phase of tetramethoxypyrene and tetracyanoquinodimethane (TMP -TCNQ ) on gold have been studied using ultraviolet photoelectron spectroscopy (UPS), x-ray diffraction (XRD), infrared (IR) spectroscopy, and scanning tunneling spectroscopy (STS......). The formation of an intermolecular charge-transfer (CT) compound is evident from the appearance of new reflexes in XRD (d =0.894nm and d =0.677nm). A softening of the CN stretching vibration (redshift by 7 cm⊃-1) of TCNQ is visible in the IR spectra, being indicative of a CT on the order of 0.3e from TMP...

  17. Spectral studies of new fullerene-tetrathiafulvalene based system

    International Nuclear Information System (INIS)

    Laskowska, Barbara; Lapinski, Andrzej; Graja, Andrzej; Hudhomme, Pietrick

    2007-01-01

    Molecular and electronic structures as well as electronic and vibrational spectra of compounds 1-3 were investigated. The spectra were recorded in the large spectral range from 400 to 50,000 cm -1 ; our interest was focused on the electronic excitations of both moieties of the dyad and the intramolecular vibrations of the dyad's components. With the help of the Gaussian 03 program, molecular geometry, electron structure and normal mode analysis for the dyad and/or reference compounds were studied. An assignment of the main vibrational bands of the dyad and its reference molecules was made taking into consideration their IR and Raman spectra as well as results of the normal mode analysis. In principle, the intramolecular vibrations typical for C 60 and tetrathiafulvalene (TTF) derivatives can be found in the spectra of the dyad; the bands' frequencies are insignificantly shifted comparing with the separated molecules but their shape is usually modified. It suggests that symmetry and molecular structure of both components of the dyad are rather kept after dyad's formation but redistribution of charges occurs

  18. 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...

  19. Synthesis and characterization of alkene-extended tetrathiafulvalenes with lateral alkyne appendages

    DEFF Research Database (Denmark)

    Nielsen, Mogens Brønsted; Gisselbrecht, Jean-Paul; Thorup, Niels

    2003-01-01

    Tetrathiafulvalene (TTF) derivatives containing a diethynyl-substituted alkene spacer were synthesized and investigated for their electronic and structural properties. Co-planarity of the central diethynylethene unit and the two dithiole rings were confirmed by X-ray crystallographic analysis....

  20. C60 Recognition from Extended Tetrathiafulvalene Bis-acetylide Platinum(II) Complexes.

    Science.gov (United States)

    Bastien, Guillaume; Dron, Paul I; Vincent, Manon; Canevet, David; Allain, Magali; Goeb, Sébastien; Sallé, Marc

    2016-11-18

    The favorable spatial organization imposed by the square planar 4,4'-di(tert-butyl)-2,2'-bipyridine (dbbpy) platinum(II) complex associated with the electronic and shape complementarity of π-extended tetrathiafulvalene derivatives (exTTF) toward fullerenes is usefully exploited to construct molecular tweezers, which display good affinities for C 60 .

  1. 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 ...

  2. 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...

  3. Determination of glutamine and glutamic acid in mammalian cell cultures using tetrathiafulvalene modified enzyme electrodes.

    Science.gov (United States)

    Mulchandani, A; Bassi, A S

    1996-01-01

    Tetrathiafulvalene (TTF) mediated amperometric enzyme electrodes have been developed for the monitoring of L-glutamine and L-glutamic acid in growing mammalian cell cultures. The detection of glutamine was accomplished by a coupled enzyme system comprised of glutaminase plus glutamate oxidase, while the detection of glutamic acid was carried out by a single enzyme, glutamate oxidase. The appropriate enzyme(s) were immoblized on the Triton-X treated surface of tetrathiafulvalene modified carbon paste electrodes by adsorption, in conjunction with entrapment by an electrochemically deposited copolymer film of 1,3-phenylenediamine and resorcinol. Operating conditions for the glutamine enzyme electrode were optimized with respect to the amount of enzymes immoblized, pH, temperature and mobile phase flow rate for operation in a flow injection (FIA) system. When applied to glutamine and glutamic acid measurements in mammalian cell culture in FIA, the results obtained with enzyme electrodes were in excellent agreement with those determined by enzymatic analysis.

  4. Development of β-linked quaterthiophene and tetrathiafulvalene dimers as new organic semiconductors

    International Nuclear Information System (INIS)

    Ashizawa, Minoru; Yu, Yan; Niimura, Takuro; Tsuboi, Kazuma; Matsumoto, Hidetoshi; Tanioka, Akihiko; Mori, Takehiko

    2010-01-01

    A series of β-linked quaterthiophene and tetrathiafulvalene dimers 1-4 has been prepared. Their redox and optical properties are almost the same as the parent monomers indicative of very little interaction between the monomers. Crystal structures of 1, 2, and 4 are highly one-dimensional, in which molecular structure of 1 is planar whereas those of 2 and 4 are in a bent form.

  5. Carboxylated dithiafulvenes and tetrathiafulvalene vinylogues: synthesis, electronic properties, and complexation with zinc ions

    Directory of Open Access Journals (Sweden)

    Yunfei Wang

    2015-06-01

    Full Text Available A class of carboxyl and carboxylate ester-substituted dithiafulvene (DTF derivatives and tetrathiafulvalene vinylogues (TTFVs has been synthesized and their electronic and electrochemical redox properties were characterized by UV–vis spectroscopic and cyclic voltammetric analyses. The carboxyl-TTFV was applied as a redox-active ligand to complex with Zn(II ions, forming a stable Zn-TTFV coordination polymer. The structural, electrochemical, and thermal properties of the coordination polymer were investigated by infrared spectroscopy, cyclic voltammetry, powder X-ray diffraction, and differential scanning calorimetric analyses. Furthermore, the microscopic porosity and surface area of the Zn-TTFV coordination polymer were measured by nitrogen gas adsorption analysis, showing a BET surface of 148.2 m2 g−1 and an average pore diameter of 10.2 nm.

  6. 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.

  7. Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly.

    Science.gov (United States)

    Iyoda, Masahiko; Hasegawa, Masashi

    2015-01-01

    The construction of redox-active supramolecular assemblies based on star-shaped and radially expanded tetrathiafulvalene (TTF) oligomers with divergent and extended conjugation is summarized. Star-shaped TTF oligomers easily self-aggregate with a nanophase separation to produce supramolecular structures, and their TTF units stack face-to-face to form columnar structures using the fastener effect. Based on redox-active self-organizing supramolecular structures, conducting nanoobjects are constructed by doping of TTF oligomers with oxidants after the formation of such nanostructures. Although radical cations derived from TTF oligomers strongly interact in solution to produce a mixed-valence dimer and π-dimer, it seems to be difficult to produce nanoobjects of radical cations different from those of neutral TTF oligomers. In some cases, however, radical cations form nanostructured fibers and rods by controlling the supramolecular assembly, oxidation states, and counter anions employed.

  8. N-aryl pyrrolo-tetrathiafulvalene based ligands: synthesis and metal coordination.

    Science.gov (United States)

    Balandier, Jean-Yves; Chas, Marcos; Dron, Paul I; Goeb, Sébastien; Canevet, David; Belyasmine, Ahmed; Allain, Magali; Sallé, Marc

    2010-03-05

    A straightforward general synthetic access to N-aryl-1,3-dithiolo[4,5-c]pyrrole-2-thione derivatives 6 from acetylenedicarbaldehyde monoacetal is depicted. In addition to their potentiality as precursors to dithioalkyl-pyrrole derivatives, thiones 6 are key building blocks to N-aryl monopyrrolo-tetrathiafulvalene (MPTTF) derivatives 10. X-ray structures of four of these thiones intermediates, reminiscent of the corresponding MPTTF derivatives, are provided. When the aryl group is a binding pyridyl unit, the MPTTF derivative 10a can coordinate M(II) salts (M = Pt, Pd). The first examples of metal-directed orthogonal MPTTF-based dimers 11-14, obtained through coordination of 10a to cis-blocked square planar Pt or Pd complexes are described. Studies on the parameters influencing the dimer construction are presented, as well as first recognition properties of the resulting electron-rich clip for C(60).

  9. Investigation of the nature of the unpaired electron states in the organic semiconductor N-methyl-N-ethylmorpholinium-tetracyanoquinodimethane

    DEFF Research Database (Denmark)

    Rice, M. J.; Yartsev, V. M.; Jacobsen, Claus Schelde

    1980-01-01

    The nature of the unpaired electron states in the dimerized phase of the crystalline organic semiconductor N-methyl-N-ethylmorpholinium-tetracyanoquinodimethane [MEM(TCNQ)2] is investigated by the combined means of polarized-optical-reflectance measurements and microscopic theoretical analysis....... It is found that each unpaired electron is localized on a dimeric TCNQ unit, and it is demonstrated that the two-site molecular orbital (MO) which accommodates the unpaired electron involves internal molecular distortion of the dimeric unit. Experimental values are deduced for the intradimer π MO hopping...... integral, the TCNQ monomer ag molecular-vibration frequencies and linear-electron-molecular-vibration coupling constants, and the difference in energy of the slightly nonequivalent TCNQ monomer π MO's. The dimer charge oscillation associated with the extremely weak coupling of the unpaired electron...

  10. Evaporation temperature-tuned physical vapor deposition growth engineering of one-dimensional non-Fermi liquid tetrathiofulvalene tetracyanoquinodimethane thin films

    DEFF Research Database (Denmark)

    Sarkar, I.; Laux, M.; Demokritova, J.

    2010-01-01

    We describe the growth of high quality tetrathiofulvalene tetracyanoquinodimethane (TTF-TCNQ) organic charge-transfer thin films which show a clear non-Fermi liquid behavior. Temperature dependent angle resolved photoemission spectroscopy and electronic structure calculations show that the growth...... of TTF-TCNQ films is accompanied by the unfavorable presence of neutral TTF and TCNQ molecules. The quality of the films can be controlled by tuning the evaporation temperature of the precursor in physical vapor deposition method....

  11. Role of water in the dynamic disproportionation of Zn-based TCNQ(F4) coordination polymers (TCNQ = tetracyanoquinodimethane).

    Science.gov (United States)

    Nafady, Ayman; Le, Thanh Hai; Vo, Nguyen; Haworth, Naomi L; Bond, Alan M; Martin, Lisandra L

    2014-02-17

    Intriguingly, coordination polymers containing TCNQ(2–) and TCNQF4(2–) (TCNQ = 7,7,8,8-tetracyanoquinodimethane, TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, both designated as TCNQ(F4)(2–)) may be generated from reaction of metal ions with TCNQ(F4)•–. An explanation is now provided in terms of a solvent-dependent dynamic disproportionation reaction. A systematic study of reactions associated with TCNQ(F4) and electrochemically generated TCNQ(F4)MeCN•– and TCNQ(F4)MeCN(2–) revealed that disproportionation of TCNQ(F4)MeCN•– radical anions in acetonitrile containing a low concentration of water is facilitated by the presence of ZnMeCN(2+). Thus, while the disproportionation reaction 2TCNQ(F4)MeCN•– TCNQ(F4)MeCN + TCNQ(F4)MeCN(2–) is thermodynamically very unfavorable in this medium (Keq ≈ 9 × 10(–10); TCNQF4), the preferential precipitation of ZnTCNQ(F4)(s) drives the reaction: ZnMeCN(2+) + 2 TCNQ(F4)MeCN•– ZnTCNQ(F4)(s) + TCNQ(F4)MeCN. The concomitant formation of soluble TCNQ(F4)MeCN and insoluble ZnTCNQ(F4)(s) and the loss of TCNQ(F4)MeCN•– were verified by UV–visible and infrared spectroscopy and steady-state voltammetry. Importantly, the reverse reaction of comproportionation rather than disproportionation becomes the favored process in the presence of ≥3% (v/v) water, due to the increased solubility of solid ZnTCNQ(F4)(s). Thus, in this “wet” environment, ZnMeCN(2+) and TCNQ(F4)MeCN•– are produced from a mixture of ZnTCNQ(F4)(s) and TCNQ(F4)MeCN and with the addition of water provides a medium for synthesis of [Zn(TCNQ(F4))2(H2O)2]. An important conclusion from this work is that the redox level of TCNQ(F4)-based materials, synthesized from a mixture of metal cations and TCNQ(F4)•–, is controlled by a solvent-dependent disproportionation/comproportionation reaction that may be tuned to favor formation of solids containing the monoanion radical, the dianion, or even a mixture of both.

  12. Interplay between Organic-Organometallic Electrophores within Bis(cyclopentadienyl)Molybdenum Dithiolene Tetrathiafulvalene Complexes.

    Science.gov (United States)

    Bellec, Nathalie; Vacher, Antoine; Barrière, Frédéric; Xu, Zijun; Roisnel, Thierry; Lorcy, Dominique

    2015-05-18

    Tetrathiafulvalenes (TTF) and bis(cyclopentadienyl) molybdenum dithiolene complexes, Cp2Mo(dithiolene) complexes, are known separately to act as good electron donor molecules. For an investigation of the interaction between both electrophores, two types of complexes were synthesized and characterized. The first type has one Cp2Mo fragment coordinated to one TTF dithiolate ligand, and the second type has one TTF bis(dithiolate) bridging two Cp2Mo fragments. Comparisons of the electrochemical properties of these complexes with those of models of each separate electrophore provide evidence for their mutual influence. All of these complexes act as very good electron donors with a first oxidation potential 430 mV lower than the tetrakis(methylthio)TTF. DFT calculations suggest that the HOMO of the neutral complex and the SOMO of the cation are delocalized across the whole TTF dithiolate ligand. The X-ray crystal structure analyses of the neutral and the mono-oxidized Cp2Mo(dithiolene)(bismethylthio)TTF complexes are consistent with the delocalized assignment of the highest occupied frontier molecular orbitals. UV-vis-NIR spectroelectrochemical investigations confirm this electronic delocalization within the TTF dithiolate ligand.

  13. Synthesis, Characterization, and Self-Assembly of a Tetrathiafulvalene (TTF–Triglycyl Derivative

    Directory of Open Access Journals (Sweden)

    Sónia Pérez-Rentero

    2018-04-01

    Full Text Available In this work, we describe the synthesis, characterization, and self-assembly properties of a new tetrathiafulvalene (TTF–triglycyl low-molecular-weight (LMW gelator. Supramolecular organogels were obtained in various solvents via a heating–cooling cycle. Critical gelation concentrations (CGC (range ≈ 5–50 g/L and thermal gel-to-sol transition temperatures (Tgel (range ≈ 36–51 °C were determined for each gel. Fourier transform infrared (FT-IR spectroscopy suggested that the gelator is also aggregated in its solid state via a similar hydrogen-bonding pattern. The fibrillar microstructure and viscoelastic properties of selected gels were demonstrated by means of field-emission electron microscopy (FE-SEM and rheological measurements. As expected, exposure of a model xerogel to I2 vapor caused the oxidation of the TTF unit as confirmed by UV-vis-NIR analysis. However, FT-IR spectroscopy showed that the oxidation was accompanied with concurrent alteration of the hydrogen-bonded network.

  14. 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.

  15. Electrosynthesis of Copper-Tetracyanoquinodimethane Based on the Coupling Charge Transfer across Water/1,2-Dichloroethane Interface

    International Nuclear Information System (INIS)

    Huang, Li; Li, Pei; Pamphile, Ndagijimana; Tian, Zhong-Qun; Zhan, Dongping

    2014-01-01

    Graphical abstract: - Highlights: • Organic semiconductor CuTCNQ is synthesized through electrochemistry of liquid/liquid interface. • A coupling charge transfer (CCT) mechanism is proposed for organic electrosynthesis. • The obtained CuTCNQ has good electrochemical and electronic properties. - Abstract: The organic salt Copper-Tetracyanoquinodimethane (CuTCNQ) is an important semiconductor used in electronics for field-effect transistors, switches and memory devices. Here we present a novel electrosynthetic method of CuTCNQ microneedles based on the coupling charge transfer across water/1,2-dichloroethane (W/1,2-DCE) interface. A HOPG electrode is covered by a small volume of 1,2-DCE solution, which is further covered by an aqueous solution to construct the W/1,2-DCE interface. When TCNQ in 1,2-DCE phase is reduced on HOPG, Cu 2+ in the aqueous solution will transfer across the W/1,2-DCE interface in order to maintain the electric neutrality. Therein CuTCNQ microneedles are formed which have good solid-state electrochemical and electronic properties. This coupling charge transfer mechanism is valuable and broadens the applications of liquid/liquid interface in organic electrosynthesis

  16. A comprehensive study of extended tetrathiafulvalene cruciform molecules for molecular electronics: synthesis and electrical transport measurements.

    Science.gov (United States)

    Parker, Christian R; Leary, Edmund; Frisenda, Riccardo; Wei, Zhongming; Jennum, Karsten S; Glibstrup, Emil; Abrahamsen, Peter Bæch; Santella, Marco; Christensen, Mikkel A; Della Pia, Eduardo Antonio; Li, Tao; Gonzalez, Maria Teresa; Jiang, Xingbin; Morsing, Thorbjørn J; Rubio-Bollinger, Gabino; Laursen, Bo W; Nørgaard, Kasper; van der Zant, Herre; Agrait, Nicolas; Nielsen, Mogens Brøndsted

    2014-11-26

    Cruciform-like molecules with two orthogonally placed π-conjugated systems have in recent years attracted significant interest for their potential use as molecular wires in molecular electronics. Here we present synthetic protocols for a large selection of cruciform molecules based on oligo(phenyleneethynylene) (OPE) and tetrathiafulvalene (TTF) scaffolds, end-capped with acetyl-protected thiolates as electrode anchoring groups. The molecules were subjected to a comprehensive study of their conducting properties as well as their photophysical and electrochemical properties in solution. The complex nature of the molecules and their possible binding in different configurations in junctions called for different techniques of conductance measurements: (1) conducting-probe atomic force microscopy (CP-AFM) measurements on self-assembled monolayers (SAMs), (2) mechanically controlled break-junction (MCBJ) measurements, and (3) scanning tunneling microscopy break-junction (STM-BJ) measurements. The CP-AFM measurements showed structure-property relationships from SAMs of series of OPE3 and OPE5 cruciform molecules; the conductance of the SAM increased with the number of dithiafulvene (DTF) units (0, 1, 2) along the wire, and it increased when substituting two arylethynyl end groups of the OPE3 backbone with two DTF units. The MCBJ and STM-BJ studies on single molecules both showed that DTFs decreased the junction formation probability, but, in contrast, no significant influence on the single-molecule conductance was observed. We suggest that the origins of the difference between SAM and single-molecule measurements lie in the nature of the molecule-electrode interface as well as in effects arising from molecular packing in the SAMs. This comprehensive study shows that for complex molecules care should be taken when directly comparing single-molecule measurements and measurements of SAMs and solid-state devices thereof.

  17. Anderson-Type Polyoxometalates Functionalized by Tetrathiafulvalene Groups: Synthesis, Electrochemical Studies, and NLO Properties.

    Science.gov (United States)

    Boulmier, Amandine; Vacher, Antoine; Zang, Dejin; Yang, Shu; Saad, Ali; Marrot, Jérôme; Oms, Olivier; Mialane, Pierre; Ledoux, Isabelle; Ruhlmann, Laurent; Lorcy, Dominique; Dolbecq, Anne

    2018-04-02

    Three polyoxometalates (POMs) functionalized by tetrathiafulvalene (TTF) molecules have been synthesized by a coupling reaction between the Anderson-type POMs [MnMo 6 O 18 {(OCH 2 ) 3 CNH 2 } 2 ] 3- or [AlMo 6 O 18 (OH) 3 {(OCH 2 ) 3 CNH 2 }] 3- and the TTF carboxylic acid derivative (MeS) 3 TTF(S-CH 2 -CO 2 H). The monofunctionalized TTF-AlMo 6 POM contains one TTF group covalently grafted on an Al Anderson platform. The symmetrical TTF-MnMo 6 -TTF POM possesses two TTF groups grafted on each side of a Mn Anderson derivative while the asymmetrical TTF-MnMo 6 -SP POM contains a TTF and a spiropyran groups. These three trianionic species have been characterized by elemental analysis, 1 H and 13 C NMR, FT-IR spectroscopy, ESI-MS spectrometry, and single-crystal X-ray diffraction (for TTF-MnMo 6 -TTF). In the solid state, the grafted TTF molecules of TTF-MnMo 6 -TTF POMs interact via S···S and π···π interactions and form chains. The electrochemical properties of the complexes reflect the contributions of both the inorganic POM and the TTF moieties. Despite adsorption of the oxidized hybrid species on the Pt grid working electrode, UV-vis-NIR spectroelectrochemical investigations evidence peaks characteristic of the oxidation of the TTF units. Finally, hyper-Rayleigh scattering (HRS) measurements show that the three novel TTF derivatives exhibit β values between 20 and 37 × 10 -30 esu. Moreover it is observed that the oxidation of the TTF moieties by Fe 3+ ions increases the NLO response. These values are in the order of magnitude of that found for the well-known 4-dimethylamino- N-methyl-4-stilbazolium (DAS + ) cation (β = 60 × 10 -30 esu).

  18. Importance of Vibronic Effects in the UV-Vis Spectrum of the 7,7,8,8-Tetracyanoquinodimethane Anion.

    Science.gov (United States)

    Tapavicza, Enrico; Furche, Filipp; Sundholm, Dage

    2016-10-11

    We present a computational method for simulating vibronic absorption spectra in the ultraviolet-visible (UV-vis) range and apply it to the 7,7,8,8-tetracyanoquinodimethane anion (TCNQ - ), which has been used as a ligand in black absorbers. Gaussian broadening of vertical electronic excitation energies of TCNQ - from linear-response time-dependent density functional theory produces only one band, which is qualitatively incorrect. Thus, the harmonic vibrational modes of the two lowest doublet states were computed, and the vibronic UV-vis spectrum was simulated using the displaced harmonic oscillator approximation, the frequency-shifted harmonic oscillator approximation, and the full Duschinsky formalism. An efficient real-time generating function method was implemented to avoid the exponential complexity of conventional Franck-Condon approaches to vibronic spectra. The obtained UV-vis spectra for TCNQ - agree well with experiment; the Duschinsky rotation is found to have only a minor effect on the spectrum. Born-Oppenheimer molecular dynamics simulations combined with calculations of the electronic excitation energies for a large number of molecular structures were also used for simulating the UV-vis spectrum. The Born-Oppenheimer molecular dynamics simulations yield a broadening of the energetically lowest peak in the absorption spectrum, but additional vibrational bands present in the experimental and simulated quantum harmonic oscillator spectra are not observed in the molecular dynamics simulations. Our results underline the importance of vibronic effects for the UV-vis spectrum of TCNQ - , and they establish an efficient method for obtaining vibronic spectra using a combination of linear-response time-dependent density functional theory and a real-time generating function approach.

  19. Extension of the charge separated-state lifetime by supramolecular association of a tetrathiafulvalene electron donor to a zinc/gold bisporphyrin.

    Science.gov (United States)

    Boixel, Julien; Fortage, Jérôme; Blart, Errol; Pellegrin, Yann; Hammarström, Leif; Becker, Hans-Christian; Odobel, Fabrice

    2010-02-14

    Supramolecular triads were prepared by self-assembly of 4'-pyridyl-2-tetrathiafulvalene axially bound on ZnP-spacer-AuP(+) dyads; the lifetime of the charge separated state ((+)TTF-ZnP-Spacer-AuP ) formed upon light excitation of the triad is greatly increased with respect to that found in the parent dyad.

  20. In the search of an electron transfer between π-donors and C60: the bis-linking of tetrathiafulvalene (TTF) to C60

    International Nuclear Information System (INIS)

    Hudhomme, P.; Rabreau, J.M.; Cariou, M.; Jubault, M.; Gorgues, A.

    1998-01-01

    In order to realize the bis-linking of tetrathiafulvalene (TTF) to one or two C 60 , and to reach the dyad compounds 1 and 2, the [4+2] Diels-Alder reactions of C 60 with orthoquinodimethanic derivatives of 1,3-dithioles 5a,b or TTF 9 are studied. (orig.)

  1. π-Extended tetrathiafulvalene BODIPY (ex-TTF-BODIPY): A redox switched "on-off-on" electrochromic system with two near-infrared fluorescent outputs

    DEFF Research Database (Denmark)

    Bill, N. L.; Lim, J. M.; Davis, C. M.

    2014-01-01

    A pi-extended tetrathiafulvalene-boradiazaindacene chimera, ex-TTF-BODIPY, has been prepared. The resulting system undergoes sequential one-electron oxidations, allowing access to both the mono-oxidized radical cationic and dicationic states. Additionally, ex-TTF-BODIPY displays electrochromic...

  2. Fabrication of the tetrathiafulvalene–2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane charge transfer complex with high crystallinity by eutectic melting method

    Science.gov (United States)

    Kim, Jueun; Kang, Youngjong; Lee, Jaejong

    2018-06-01

    We show that high crystallinity and charge transporting gain can be obtained in a noble donor–acceptor system (CT complex) composed of organic complex: tetrathiafulvalene–2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (TTF–F4TCNQ). The complex is small-gap organic metallic or semiconductor (less than 1 eV), and we predict having a high conductivity. We perform an approach to fabricate organic CT complex with high crystallinity by eutectic melting method. Our process is simple and shows crystal growth with improved crystallinity when combined with soft-lithography.

  3. Charge transfer in the novel donor–acceptor complexes tetra- and hexamethoxypyrene with tetracyanoquinodimethane studied by HAXPES

    International Nuclear Information System (INIS)

    Medjanik, K.; Gloskovskii, A.; Kutnyakhov, D.; Felser, C.; Chercka, D.; Baumgarten, M.; Müllen, K.; Schönhense, G.

    2012-01-01

    Highlights: ► The effect of charge transfer in TMP/HMP–TCNQ complexes was studied using HAXPES. ► We examine changes in the core level spectra of TMP/HMP–TCNQ complexes. ► The charge is transferred to a fraction of 60% of the molecules in the complexes. - Abstract: The effect of charge transfer (CT) in complexes of the donors tetra- and hexamethoxyprene (TMP and HMP) with the classical acceptor tetracyanoquinodimethane (TCNQ) was studied using hard X-ray photoemission (HAXPES). Microcrystals of the complex were grown via vapour diffusion from donor–acceptor mixtures. The bulk sensitivity of HAXPES at a photon energy of 6 keV completely eliminates the problem of surface contamination for such delicate organic materials grown from solution. The donor molecules were produced using a novel synthesis route functionalizing polycyclic aromatic hydrocarbons at their periphery. For comparison, spectra were also taken from thin-film samples of the same compounds produced via co-deposition in UHV. Upon complex formation, the oxygen 1s core-level spectra (being a fingerprint of the methoxy-group of the donors) change from the single-line spectrum of pure HMP (TMP) to a spectrum with two distinct lines shifted by 1.4 (0.9) eV and 2.6 (2.3) eV with respect to the position of the oxygen 1s line of the pure donors. The nitrogen 1s spectra (being a fingerprint of the cyano-group in the acceptor) show two peaks as well with a corresponding shift of 0.9 eV and 2.0 eV in comparison with the leading line of pure TCNQ in opposite direction to the oxygen 1s spectra. These values are substantially larger than shifts in near edge X-ray absorption fine structure (NEXAFS) and ultraviolet photoelectron spectroscopy (UPS) spectra of the same complexes. The changes in the spectra are discussed in terms of the CT in the complexes. Residues of pure donor and acceptor materials in the microcrystal fractions of the complexes are evident from the presence of non-shifted lines. Peak

  4. Sulfite oxidase biosensors based on tetrathiafulvalene modified screen-printed carbon electrodes for sulfite determination in wine.

    Science.gov (United States)

    Molinero-Abad, Begoña; Alonso-Lomillo, M Asunción; Domínguez-Renedo, Olga; Arcos-Martínez, M Julia

    2014-02-17

    Screen-printed carbon electrodes have been modified with tetrathiafulvalene and sulfite oxidase enzyme for the sensitive and selective detection of sulfite. Amperometric experimental conditions were optimized taking into account the importance of quantifying sulfite in wine samples and the inherent complexity of these samples, particularly red wine. The biosensor responds to sulfite giving a cathodic current (at +200 mV vs screen-printed Ag/AgCl electrode and pH 6) in a wide concentration range, with a capability of detection of 6 μM (α=β=0.05) at 60°C. The method has been applied to the determination of sulfite in white and red samples, with averages recoveries of 101.5% to 101.8%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Incorporation of fused tetrathiafulvalenes (TTFs) into polythiophene architectures: varying the electroactive dominance of the TTF species in hybrid systems.

    Science.gov (United States)

    Berridge, Rory; Skabara, Peter J; Pozo-Gonzalo, Cristina; Kanibolotsky, Alexander; Lohr, Jan; McDouall, Joseph J W; McInnes, Eric J L; Wolowska, Joanna; Winder, Christoph; Sariciftci, N Serdar; Harrington, Ross W; Clegg, William

    2006-02-23

    A novel polythienylenevinylene (PTV) and two new polythiophenes (PTs), featuring fused tetrathiafulvalene (TTF) units, have been prepared and characterized by ultraviolet-visible (UV-vis) and electron paramagnetic resonance (EPR) spectroelectrochemistry. All polymers undergo two sequential, reversible oxidation processes in solution. Structures in which the TTF species is directly linked to the polymer backbone (2 and 4) display redox behavior which is dictated by the fulvalene system. Once the TTF is spatially removed from the polymer chain by a nonconjugated link (polymer 3), the electroactivity of both TTF and polythiophene moieties can be detected. Computational studies confirm the delocalization of charge over both electroactive centers (TTF and PT) and the existence of a triplet dication intermediate. PTV 4 has a low band gap (1.44 eV), is soluble in common organic solvents, and is stable under ambient conditions. Organic solar cells of polymer 4:[6,6]-phenyl-C(61) butyric acid methyl ester (PCBM) have been fabricated. Under illumination, a photovoltaic effect is observed with a power conversion efficiency of 0.13% under AM1.5 solar simulated light. The onset of photocurrent at 850 nm is consistent with the onset of the pi-pi absorption band of the polymer. Remarkably, UV-vis spectroelectrochemistry of polymer 4 reveals that the conjugated polymer chain remains unchanged during the oxidation of the polymer.

  6. CNT fibers p-doped with F4TCNQ (2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane)

    Science.gov (United States)

    Lepak, Sandra; Boncel, Sławomir; Jóźwik, Iwona; Jakubowska, Małgorzata; Koziol, Krzysztof; Łekawa-Raus, Agnieszka

    2017-08-01

    Films and fibers made of carbon nanotubes were found to be promising materials for future electrical and electronic engineering. Despite of many advantages provided by these materials, they are not without problems. The biggest issue is that the macroscopic CNT structures, such as films or fibers, have much lower electrical conductivity values than it is for individual carbon nanotubes. And therefore researchers worldwide try to increase electrical properties of those macroscopic structures. One of the approaches scientists are currently investigating is chemical doping. Despite chemical doping has been already reported there is still a huge list of compounds that are capable to increase the conductivity values and has not been tested yet. In this work one of such compounds has been examined. It is a strong p-dopant 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). The solution of F4TCNQ in three different solvents (chloroform, acetic acid and dimethylsulfoxide) has been prepared and applied on purified CNT films. Both electrical conductivity and specific conductivity was measured. The best electrical conductivity value achieved is 5,24·106 S·m-1. Samples were also observed under SEM.

  7. A flow cell for transient voltammetry and in situ grazing incidence X-ray diffraction characterization of electrocrystallized cadmium(II) tetracyanoquinodimethane

    Energy Technology Data Exchange (ETDEWEB)

    Veder, Jean-Pierre [Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box U1987, Perth, Western Australia 6845 (Australia); Nafady, Ayman [School of Chemistry, Monash University, Clayton, Victoria 3800 (Australia); Clarke, Graeme [Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box U1987, Perth, Western Australia 6845 (Australia); Williams, Ross P. [Centre for Materials Research, Department of Imaging and Applied Physics, Curtin University, GPO Box U1987, Perth, Western Australia 6845 (Australia); De Marco, Roland, E-mail: r.demarco@curtin.edu.a [Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box U1987, Perth, Western Australia 6845 (Australia); Bond, Alan M. [School of Chemistry, Monash University, Clayton, Victoria 3800 (Australia)

    2011-01-01

    An easy to fabricate and versatile cell that can be used with a variety of electrochemical techniques, also meeting the stringent requirement for undertaking cyclic voltammetry under transient conditions in in situ electrocrystallization studies and total external reflection X-ray analysis, has been developed. Application is demonstrated through an in situ synchrotron radiation-grazing incidence X-ray diffraction (SR-GIXRD) characterization of electrocrystallized cadmium (II)-tetracyanoquinodimethane material, Cd(TCNQ){sub 2}, from acetonitrile (0.1 mol dm{sup -3} [NBu{sub 4}][PF{sub 6}]). Importantly, this versatile cell design makes SR-GIXRD suitable for almost any combination of total external reflection X-ray analysis (e.g., GIXRF and GIXRD) and electrochemical perturbation, also allowing its application in acidic, basic, aqueous, non-aqueous, low and high flow pressure conditions. Nevertheless, the cell design separates the functions of transient voltammetry and SR-GIXRD measurements, viz., voltammetry is performed at high flow rates with a substantially distended window to minimize the IR (Ohmic) drop of the electrolyte, while SR-GIXRD is undertaken using stop-flow conditions with a very thin layer of electrolyte to minimize X-ray absorption and scattering by the solution.

  8. Efficiency enhancement of tandem organic light-emitting devices by a combined charge generation layer and organic n-type bis(ethylenedithio)-tetrathiafulvalene-doped electron transport layer

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Jin Taek; Kim, Dae Hun; Koh, Eun Im; Kim, Tae Whan

    2014-11-03

    While the operating voltage of the tandem organic light-emitting devices (OLEDs) with both an organic p-type 1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile charge generation layer and a bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF)-doped 1,3,5-tris(N-phenylbenzimiazole-2-yl)benzene (TPBi) electron transport layer (ETL) was 1.3 V lower than that of the tandem OLEDs with a BEDT-TTF-undoped TPBi ETL. Luminance efficiency of the tandem OLEDs with a BEDT-TTF-doped TPBi ETL was 3.6 cd/A higher than that of the typical OLEDs. The increase in the luminance efficiency and the decrease in the operating voltage of the tandem OLEDs were attributed to improved electron injection due to the insertion of the BEDT-TTF-doped TPBi ETL. - Highlights: • Tandem organic light-emitting diodes (OLED) were fabricated. • OLED fabricated with an n-type bis(ethylenedithio)-tetrathiafulvalene. • Operating voltage of the tandem OLED was decreased from 19.8 to 18.5 V. • Luminance efficiency of the tandem OLED was increased from 31.8 to 35.4 cd/A. • Enhancement of the luminance efficiency in the tandem OLED was achieved.

  9. Efficiency enhancement of tandem organic light-emitting devices by a combined charge generation layer and organic n-type bis(ethylenedithio)-tetrathiafulvalene-doped electron transport layer

    International Nuclear Information System (INIS)

    Cho, Jin Taek; Kim, Dae Hun; Koh, Eun Im; Kim, Tae Whan

    2014-01-01

    While the operating voltage of the tandem organic light-emitting devices (OLEDs) with both an organic p-type 1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile charge generation layer and a bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF)-doped 1,3,5-tris(N-phenylbenzimiazole-2-yl)benzene (TPBi) electron transport layer (ETL) was 1.3 V lower than that of the tandem OLEDs with a BEDT-TTF-undoped TPBi ETL. Luminance efficiency of the tandem OLEDs with a BEDT-TTF-doped TPBi ETL was 3.6 cd/A higher than that of the typical OLEDs. The increase in the luminance efficiency and the decrease in the operating voltage of the tandem OLEDs were attributed to improved electron injection due to the insertion of the BEDT-TTF-doped TPBi ETL. - Highlights: • Tandem organic light-emitting diodes (OLED) were fabricated. • OLED fabricated with an n-type bis(ethylenedithio)-tetrathiafulvalene. • Operating voltage of the tandem OLED was decreased from 19.8 to 18.5 V. • Luminance efficiency of the tandem OLED was increased from 31.8 to 35.4 cd/A. • Enhancement of the luminance efficiency in the tandem OLED was achieved

  10. 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

    The synthesis and X-ray crystal structure of the ethane-linked dimeric tetrathiafulvalene [(EDT-TTF-CH2)(2)], 1,2-bis(ethylenedithiotetrathiafulvalenyl)ethane (1), is reported. It oxidizes reversibly at 0.45 and 0.90 V vs SCE. Electrocrystallization in the presence of [n-Bu4N][FeCl4] or [n-Bu4N...

  11. 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.

  12. Charge-Transfer Supra-Amphiphiles Built by Water-Soluble Tetrathiafulvalenes and Viologen-Containing Amphiphiles: Supramolecular Nanoassemblies with Modifiable Dimensions.

    Science.gov (United States)

    Lv, Zhong-Peng; Chen, Bin; Wang, Hai-Ying; Wu, Yue; Zuo, Jing-Lin

    2015-08-05

    In this study, multidimensional nanoassemblies with various morphologies such as nanosheets, nanorods, and nanofibers are developed via charge-transfer interaction and supra-amphiphile self-assembling in aqueous phase. The charge-transfer interactions between tetrathiafulvalene derivatives (TTFs) and methyl viologen derivatives (MVs) have been confirmed by the characteristic charger-transfer absorption. (1) H NMR and electrospray ionizsation mass spectrometry (ESI-MS) analyses also indicate supra-amphiphiles are formed by the combination of TTFs and MVs head group through charge-transfer interaction and Coulombic force. X-ray single crystal structural studies, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) reveal that both linkage pattern of TTFs in hydrophilic part and alkane chain structure in hydrophobic part have significant influence on nanoassemblies morphology and microstructure. Moreover, gold nanoparticles (AuNPs) are introduced in the above supramolecular nanoassemblies to construct a supra-amphiphile-driven organic-AuNPs assembly system. AuNPs could be assembled into 1D-3D structures by adding different amount of MVs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. A scanning tunneling microscope study on an ordered mixed monolayer of bis(4,5-dihydronaphtho[1,2-d])-tetrathiafulvalene and n-tetradecane on highly oriented pyrolytic graphite.

    Science.gov (United States)

    Zhao, Miao; Jiang, Peng; Deng, Ke; Jiang, Chao

    2010-11-01

    Tetrathiafulvalene (TTF) and its derivatives (TTFs) have been successfully used as building blocks to form charge transfer salts and organic semiconductors because of their special structures and rich electron nature. We report the formation of ordered mixed binary-component monolayer consisting of Bis(4,5-dihydronaphtho[1,2-d])tetrathiafulvalene (DH-TTF) and n-tetradecane (n-C14H30) molecules on highly oriented pyrolytic graphite (HOPG) surface. Scanning tunneling microscope (STM) imaging reveals that the two different kinds of molecules can spontaneously form ordered periodic phase separation structures on the substrate, in which ordered DH-TTF double- (or single-) lamella structures are periodically tuned by ordered n-C14H30 double- (or single-) lamella structures. Furthermore, scanning tunneling spectrum (STS) measurements by addressing the individual DH-TTF and n-C14H30 molecules in the ordered monolayer show that the two different kinds of molecules exhibit completely different I(V) characters on the HOPG substrate. The modulated arrangement of the TTF derivative by insulating molecules opens a possible route to construct organic conducting molecule ribbons for potential application in nanodevices.

  14. Magnetic and Photo-Physical Properties of Lanthanide Dinuclear Complexes Involving the 4,5-Bis(2-Pyridyl-N-Oxidemethylthio-4′,5′-Dicarboxylic Acid-Tetrathiafulvalene-, Dimethyl Ester Ligand

    Directory of Open Access Journals (Sweden)

    Fabrice Pointillart

    2015-12-01

    Full Text Available The reaction between the 4,5-bis(2-pyridyl-N-oxidemethylthio-4′,5′-dicarboxylic acid-tetrathiafulvalene-, dimethyl ester ligand (L and the metallo-precursors Ln(hfac3·2H2O leads to the formation of two dinuclear complexes of formula [Ln2(hfac6(L]·(CH2Cl2·(C6H140.5 (LnIII = DyIII (1 and YbIII (2. The X-ray structure reveals a quite regular square anti-prism symmetry for the coordination sphere of the lanthanide ion. UV-visible absorption properties have been experimentally measured and rationalized by TD-DFT calculations. The functionalization of the tetrathiafulvalene (TTF core by two methyl ester moieties induces the appearance of an additional absorption band in the lowest-energy region of the spectrum. The latter has been identified as a HOMO (Highest Occupied Molecular Orbital→LUMO (Lowest Unoccupied Molecular Orbital Intra-Ligand Charge Transfer (ILCT transition in which the HOMO and LUMO are centred on the TTF and methyl ester groups, respectively. Irradiation at 22,222 cm−1 of this ILCT band induces an efficient sensitization of the YbIII-centred emission that can be correlated to the magnetic properties.

  15. Organic charge transfer phase formation in thin films of the BEDT-TTF/TCNQ donor-acceptor system

    DEFF Research Database (Denmark)

    Solovyeva, Vita; Keller, K.; Huth, M.

    2009-01-01

    We have performed charge transfer phase formation studies on the donor/acceptor system bis-(ethylendithio)tetrathiafulvalene (BEDT-TTF)/tetracyanoquinodimethane,(TCNQ) by means of physical vapor deposition. We prepared donor/acceptor bilayer structures on glass and Si(100)/SiO substrates held...

  16. 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...

  17. Organic Semiconductors and Conductors with tert-Butyl Substituents

    Directory of Open Access Journals (Sweden)

    Toshiki Higashino

    2012-08-01

    Full Text Available Tetrathiafulvalene (TTF, pentacene, and quarterthiophene with tert-butyl substituents are synthesized, and the crystal structures and the transistor properties are investigated. The tetracyanoquinodimethane (TCNQ complex of tert-butyl TTF constructs highly one-dimensional segregated columns with tetragonal crystal symmetry.

  18. Hybrid molecular materials based upon organic pi-electron donors and inorganic metal complexes. Conducting salts of bis(ethylenediseleno)tetrathiafulvalene (BEST) with the octahedral anions hexacyanoferrate(III) and nitroprusside

    CERN Document Server

    Clemente-Leon, M; Galan-Mascaros, J R; Giménez-Saiz, C; Gómez-García, C J; Fabre, J M; Mousdis, G A; Papavassiliou, G C

    2002-01-01

    The synthesis, structure and physical characterization of three new radical salts formed by the organic donor bis(ethylenediseleno)tetrathiafulvalene (BEDS-TTF or BEST) and the paramagnetic hexacyanoferrate(III) anion [Fe(CN) sub 6] sup 3 sup - or the photochromic nitroprusside anion [Fe(CN) sub 5 NO] sup 2 sup - are reported: (BEST) sub 4 [Fe(CN) sub 6] (1), (BEST) sub 3 [Fe(CN) sub 6] sub 2 centre dot H sub 2 O (2) and (BEST) sub 2 [Fe(CN) sub 5 NO] (3). Salts 1 and 3 show a layered structure with alternating organic (beta-type packing) and inorganic slabs. Salt 2 shows an original interpenetrated structure probably due to the unprecedented presence of (BEST) sup 2 sup + dications. The three salts are semiconductors although salt 1 exhibits a high room temperature conductivity and a semiconducting-semiconducting transition at ca. 150 K which has been attributed to a dimerization in the organic sublattice.

  19. Mass Spectra of Tetraselenafulvalenes, Diselenadithiafulvalenes and Tetrathiafulvalenes

    DEFF Research Database (Denmark)

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

    1978-01-01

    fragmentation of the molecular ion, as the selenium fulvalenes lose an alkyne molecule, whereas the sulphur fulvalenes first lose an (SĊR) radical. An important feature of the spectra of the simple heterofulvalenes is the formation of a rearrangement ion by migration of a heteroatom. The mechanism...

  20. Optical properties of double-layer structure phthalocyanine-tetracyanoquinodimethane

    Czech Academy of Sciences Publication Activity Database

    Bortchagovsky, E. G.; Kazantseva, Z. I.; Koshets, I. A.; Nešpůrek, Stanislav; Jastrabík, Lubomír

    2004-01-01

    Roč. 460, 1-2 (2004), s. 269-273 ISSN 0040-6090 R&D Projects: GA AV ČR IAA1050901; GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : organic semiconductors * ellipsometry * optical spectroscopy Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.647, year: 2004

  1. Molecular recognition applied to gas detection: the contribution of Langmuir-Blodgett films

    International Nuclear Information System (INIS)

    Clemendot, Sylvain

    1992-01-01

    In the first part of this research thesis, the author presents the Langmuir-Blodgett technique and outlines how it can face the challenge of molecular electronics. Then, he proposes an overview of the state-of-the-art of chemical sensors based on LB films, and an assessment of the state of the art of conductive LB films based on TCNQ (tetracyanoquinodimethane) and on tetrathiafulvalene for which the author proposes a modelling. He describes how phosphine sensors with varying conductivity based on TCNQ-based conductive LB films have been developed and reports the study of electric performance of these sensors. He describes and compares mechanisms of interaction of phosphine with conductive LB films for films based on TCNQ and those based on tetrathiafulvalene [fr

  2. Thin films of molecular metals TTF-TCNQ

    International Nuclear Information System (INIS)

    Fraxedas, J.; Molas, S.; Figueras, A.; Jimenez, I.; Gago, R.; Auban-Senzier, P.; Goffman, M.

    2002-01-01

    We present recent results on the characterization of highly ordered polycrystalline thin films of the charge transfer salt TTF-TCNQ (TTF=tetrathiafulvalene, TCNQ=tetracyanoquinodimethane) prepared by thermal sublimation in high vacuum under different conditions. The increase in orientation and microcrystal size as a function of substrate and annealing temperatures is addressed. A consequence of such an increase is the reduction of the conductivity activation energy, which eventually leads to the observation of the Peierls transition by resistivity measurements. X-ray absorption near edge spectroscopy studies performed with synchrotron radiation reveal directly the influence of charge transfer on unoccupied states near the Fermi level

  3. Thin films of molecular metals TTF-TCNQ

    CERN Document Server

    Fraxedas, J; Figueras, A; Jimenez, I; Gago, R; Auban-Senzier, P; Goffman, M

    2002-01-01

    We present recent results on the characterization of highly ordered polycrystalline thin films of the charge transfer salt TTF-TCNQ (TTF=tetrathiafulvalene, TCNQ=tetracyanoquinodimethane) prepared by thermal sublimation in high vacuum under different conditions. The increase in orientation and microcrystal size as a function of substrate and annealing temperatures is addressed. A consequence of such an increase is the reduction of the conductivity activation energy, which eventually leads to the observation of the Peierls transition by resistivity measurements. X-ray absorption near edge spectroscopy studies performed with synchrotron radiation reveal directly the influence of charge transfer on unoccupied states near the Fermi level.

  4. Four-electron transfer tandem tetracyanoquinodimethane for cathode-active material in lithium secondary battery

    Science.gov (United States)

    Kurimoto, Naoya; Omoda, Ryo; Mizumo, Tomonobu; Ito, Seitaro; Aihara, Yuichi; Itoh, Takahito

    2018-02-01

    Quinoid compounds are important candidates of organic active materials for lithium-ion batteries. However, its high solubility to organic electrolyte solutions and low redox potential are known as their major drawbacks. To circumvent these issues, we have designed and synthesized a tandem-tetracyanoquinonedimethane type cathode-active material, 11,11,12,12,13,13,14,14-octacyano-1,4,5,8-anthradiquinotetramethane (OCNAQ), that has four redox sites per molecule, high redox potential and suppressed solubility to electrolyte solution. Synthesized OCNAQ has been found to have two-step redox reactions by cyclic voltammetry, and each step consists of two-electron reactions. During charge-discharge tests using selected organic cathode-active materials with a lithium metal anode, the cell voltages obtained from OCNAQ are higher than those for 11,11-dicyanoanthraquinone methide (AQM) as expected, due to the strong electron-withdrawing effect of the cyano groups. Unfortunately, even with the use of the organic active material, the issue of dissolution to the electrolyte solution cannot be suppressed completely; however, appropriate choice of the electrolyte solutions, glyme-based electrolyte solutions in this study, give considerable improvement of the cycle retention (98% and 56% at 10 and 100 cycles at 0.5C, respectively). The specific capacity and energy density obtained in this study are 206 mAh g-1 and 554 mWh g-1 with respect to the cathode active material.

  5. Small molecules make big differences: molecular doping effects on electronic and optical properties of phosphorene

    International Nuclear Information System (INIS)

    Jing, Yu; Tang, Qing; He, Peng; Zhou, Zhen; Shen, Panwen

    2015-01-01

    Systematical computations on the density functional theory were performed to investigate the adsorption of three typical organic molecules, tetracyanoquinodimethane (TCNQ), tetracyanoethylene (TCNE) and tetrathiafulvalene (TTF), on the surface of phosphorene monolayers and thicker layers. There exist considerable charge transfer and strong non-covalent interaction between these molecules and phosphorene. In particular, the band gap of phosphorene decreases dramatically due to the molecular modification and can be further tuned by applying an external electric field. Meanwhile, surface molecular modification has proven to be an effective way to enhance the light harvesting of phosphorene in different directions. Our results predict a flexible method toward modulating the electronic and optical properties of phosphorene and shed light on its experimental applications. (paper)

  6. Pseudo-Jahn-Teller Distortion in Two-Dimensional Phosphorus: Origin of Black and Blue Phases of Phosphorene and Band Gap Modulation by Molecular Charge Transfer.

    Science.gov (United States)

    Chowdhury, Chandra; Jahiruddin, Sheik; Datta, Ayan

    2016-04-07

    Phosphorene (Pn) is stabilized as a layered material like graphite, yet it possess a natural direct band gap (Eg = 2.0 eV). Interestingly, unlike graphene, Pn exhibits a much richer phase diagram which includes distorted forms like the stapler-clip (black Pn, α form) and chairlike (blue Pn, β form) structures. The existence of these phases is attributed to pseudo-Jahn-Teller (PJT) instability of planar hexagonal P6(6-) rings. In both cases, the condition for vibronic instability of the planar P6(6-) rings is satisfied. Doping with electron donors like tetrathiafulvalene and tetraamino-tetrathiafulvalene and electron acceptors like tetracyanoquinodimethane and tetracyanoethylene convert blue Pn into N-type and black Pn into efficient P-type semiconductors, respectively. Interestingly, pristine blue Pn, an indirect gap semiconductor, gets converted into a direct gap semiconductor on electron or hole doping. Because of comparatively smaller undulation in blue Pn (with respect to black Pn), the van der Waals interactions between the dopants and blue Pn is stronger. PJT distortions for two-dimensional phosphorus provides a unified understanding of structural features and chemical reactivity in its different phases.

  7. 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

    -functionalized MPTTF/BPTTF derivatives, two different tailor-made amino acids, and C-60. Electronic communication between the MPTTF/BPTTF units and the C-60 moieties was studied by a variety of techniques including cyclic voltammetry and absorption spectroscopy. These solution-based studies indicated no observable...

  8. Tetrathiafulvalene-Oligo(para-phenyleneethynylene) Conjugates: Formation of Multiple Mixed-Valence Complexes upon Electrochemical Oxidation

    Czech Academy of Sciences Publication Activity Database

    Lipnická, Šárka; Bělohradský, Martin; Kolivoška, Viliam; Pospíšil, Lubomír; Hromadová, Magdaléna; Pohl, Radek; Vacek Chocholoušová, Jana; Vacek, Jaroslav; Fiedler, Jan; Stará, Irena G.; Starý, Ivo

    2013-01-01

    Roč. 19, č. 19 (2013), s. 6108-6121 ISSN 0947-6539 R&D Projects: GA ČR GAP207/10/2214; GA ČR GA203/09/0705; GA ČR GA203/09/1802; GA MŠk 7E09054; GA AV ČR IAA400400802 EU Projects: European Commission(XE) 213382 - FUNMOL Institutional support: RVO:61388963 ; RVO:61388955 Keywords : cross - coupling * donor-acceptor systems * tetrathiofulvalene * oligomers * electrochemistry Subject RIV: CC - Organic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W) Impact factor: 5.696, year: 2013

  9. Diels-Alder Reaction of Isobenzofurans/Cyclopentadienones with Tetrathiafulvalene: Preparation of Naphthalene, Fluoranthene, and Fluorenone Derivatives.

    Science.gov (United States)

    Karunakaran, Jayachandran; Mohanakrishnan, Arasambattu K

    2018-02-16

    Diels-Alder reaction of 1,3-diarylbenzo[c]furan/cyclopentadienone with TTF followed by triflic acid mediated cleavage of the resulting adducts led to the formation of the respective 1,4-diaryl substituted naphthalenes, fluoranthenes, and fluorenones. The photophysical properties of representative diaryl-substituted hydrocarbons are also reported.

  10. 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

    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...

  11. 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

    ) obtained by UV/Vis titrations in benzonitrile (PhCN) at room temperature. On the basis of DFT studies at the B3LYP/6-311G(d,p) level, the orbital interactions between the crown ether moieties and the p surface of the fullerene together with the endohedral Li+ have a crucial role in robust complex formation...

  12. 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...

  13. 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.

  14. 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…

  15. Self-organization of a tetrasubstituted tetrathiafulvalene (TTF) in a silica based hybrid organic-inorganic material.

    Science.gov (United States)

    Cerveau, Geneviève; Corriu, Robert J P; Lerouge, Frédéric; Bellec, Nathalie; Lorcy, Dominique; Nobili, Maurizio

    2004-02-21

    A hybrid organic inorganic nanostructured material containing a TTF core substituted by four arms exhibited a high level of both condensation at silicon (96%) and self-organization as evidenced by X-ray diffraction and an unprecedented birefringent behaviour.

  16. Synthesis and X-ray crystal structure of the first tetrathiafulvalene-based acceptor-donor-acceptor sandwich

    DEFF Research Database (Denmark)

    Simonsen, Klaus B.; Thorup, Niels; Cava, Michael P.

    1998-01-01

    The synthesis and characterization of a bis-macrocyclic A-D-A sandwich produced in a simple one-pot reaction is reported. Only one acceptor unit participates in charge-transfer interactions with the TTF unit in the solid state....

  17. Electronic and magnetic properties of TTF and TCNQ covered Co thin films

    Energy Technology Data Exchange (ETDEWEB)

    Geijn, Elmer van, E-mail: e.vangeijn@utwente.nl; Wang, Kai; Jong, Michel P. de [NanoElectronics Group, MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands)

    2016-05-07

    Interfacial effects like orbital hybridization and charge transfer strongly influence the transfer of spins from ferromagnetic metals to organic semiconductors and can lead to the formation of interfacial states with distinct magnetic properties. The changes in the electronic and magnetic properties of a thin Co film upon adsorption of a layer of either the molecular organic electron donor tetrathiafulvalene (TTF) or the acceptor tetracyanoquinodimethane (TCNQ) have been investigated by X-ray absorption spectroscopy and X-ray magnetic circular dichroism using synchrotron radiation. Clear differences between the spectra of the adsorbed molecules and the neutral molecules show the hybridization of the molecular orbitals with the Co interface. Deposition of both organic materials leads to a small increase of the ratio of the orbital magnetic moment to the spin magnetic moment of the Co atoms at the interface. The main effect of overlayer deposition is a modification of the magnetic hysteresis of the Co film: The TCNQ slightly reduces the coercivity of the Co, while the TTF increases the coercivity by a factor of ∼1.5. These complementary effects of either a molecular organic electron donor or acceptor on the interfacial properties of a metal ferromagnetic thin film are a promising result for the controlled modification of the magnetic structure of hybrid interfaces.

  18. Tuning electronic properties of graphene nanoflake polyaromatic hydrocarbon through molecular charge-transfer interactions

    Science.gov (United States)

    Sharma, Vaishali; Dabhi, Shweta D.; Shinde, Satyam; Jha, Prafulla K.

    2018-05-01

    By means of first principles calculation we have tuned the electronic properties of graphene nanoflake polyaromatic hydrocarbon via molecular charge transfer. Acceptor/donor Tetracyanoquinodimethane (TCNQ) and Tetrathiafulvalene (TTF) organic molecules are adsorbed on polyaromatic hydrocarbons (PAH) in order to introduce the charge transfer. The substrate's n- or p- type nature depends on the accepting/donating behavior of dopant molecules. Two different classes of PAH (extended form of triangulene) namely Bow-tie graphene nanoflake (BTGNF) and triangular zigzag graphene nanoflake (TZGNF). It is revealed that all the TCNQ and TTF modified graphene nanoflakes exhibit significant changes in HOMO-LUMO gap in range from 0.58 eV to 0.64 eV and 0.01 eV to 0.05 eV respectively. The adsorption energies are in the range of -0.05 kcal/mol to -2.6 kcal/mol. The change in work function is also calculated and discussed, the maximum charge transfer is for TCNQ adsorbed BTGNF. These alluring findings in the tuning of electronic properties will be advantageous for promoting graphene nanoflake polyaromatic hydrocarbon for their applications in electronic devices.

  19. Combinatorial selection of a two-dimensional 3d-TM-tetracyanoquinodimethane (TM-TCNQ) monolayer as a high-activity nanocatalyst for CO oxidation

    DEFF Research Database (Denmark)

    Deng, Qingming; Wu, Tiantian; Chen, Guibin

    2018-01-01

    catalyzed by Sc-TCNQ (CO + O2* → OOCO*) can follow the LH mechanism with free energy barriers as low as 0.73 eV at 300 K. The second step of CO + O* → CO2 can occur with rather small energy barriers via either LH or ER mechanisms. The high activity of Sc-TCNQ can be attributed to its unique structural...... and thermodynamics of all the ten candidates (Sc-Zn), Sc-TCNQ is found to display the lowest activation energies and yield the highest catalytic activity for room temperature CO oxidation. Exploring the Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms, we find that the rate-limiting step of CO oxidation...... and electronic features by possessing high stability, optimum adsorption energies with adsorbates, and fast reaction kinetics. These results have significant implications for the synthesis of two-dimensional single atom catalysis for CO oxidation with low-cost and high activity at low temperature....

  20. 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.

  1. 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

    in fluid solution at room temperature. Time-resolved transient absorption spectroscopy confirmed that the potentially luminescent MLCT states of 7-10 are significantly shorter lived than the corresponding states of the model species. Photoinduced electron-transfer processes from the TTF moieties...

  2. 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

    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...... semiconductors...

  3. Small gap semiconducting organic charge-transfer interfaces

    NARCIS (Netherlands)

    Nakano, M.; Alves, H.; Molinari, A.S.; Ono, S.; Minder, N.; Morpurgo, A.F.

    2010-01-01

    We investigated transport properties of organic heterointerfaces formed by single-crystals of two organic donor-acceptor molecules, tetramethyltetraselenafulvalene and 7,7,8,8-tetracyanoquinodimethane (TCNQ). Whereas the individual crystals have unmeasurably high resistance, the interface exhibits a

  4. A Methyl Substituted Thiophenic-TTF Donor and its Salts

    OpenAIRE

    Silva, Rafaela A. L.; Santos, Isabel C.; Lopes, Elsa B.; Rabaça, Sandra; Galindo, Sergi; Mas-Torrent, Marta; Rovira Angulo, Concepció

    2015-01-01

    α-Methyldithiophene–tetrathiafulvalene (α-mDT-TTF), the first alkyl-substituted thiophene–tetrathiafulvalene electronic donor, and some of its charge-transfer salts were explored. The crystal structure of α-mDT-TTF is composed of molecular stacks aligned parallel to each other. Its cyclic voltammetry shows higher electron-donor ability than the unsubstituted analogue. This material was employed as a semiconductor in an organic field-effect transistor and showed a mobil...

  5. The Hall effect in the organic conductor TTF–TCNQ: choice of geometry for accurate measurements of a highly anisotropic system

    DEFF Research Database (Denmark)

    Tafra, E; Čulo, M; Basletić, M

    2012-01-01

    We have measured the Hall effect on recently synthesized single crystals of the quasi-one-dimensional organic conductor TTF–TCNQ (tetrathiafulvalene–tetracyanoquinodimethane), a well known charge transfer complex that has two kinds of conductive stacks: the donor (TTF) and the acceptor (TCNQ) cha...

  6. Infrared properties of the organic semiconductor MEM(TCNQ)2 in its high-temperature phase

    DEFF Research Database (Denmark)

    Yartsev, V. M.; Jacobsen, Claus Schelde

    1981-01-01

    The infrared spectrum of N-methyl-N-ethylmorpholinium tetra-cyanoquinodimethane, MEM(TCNQ)2, at temperatures above the phase transition at T=335 K is reported. The oscillator strength associated with chargetransfer processes is shifted down in frequency as compared to the room-temperature phase. ...

  7. 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...

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

    International Nuclear Information System (INIS)

    Singleton, John; Caulfield, Jason; Hill, Stephen; Blundell, Stephen; Lubczynski, Wieslaw; House, Andrew; Hayes, William; Perenboom, Jos; Kurmoo, Mohammedally; Day, Peter

    1995-01-01

    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.)

  9. 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...

  10. Anion complexation by calix[4]arene–TTF conjugates

    Czech Academy of Sciences Publication Activity Database

    Flídrová, K.; Tkadlecová, M.; Lang, Kamil; Lhoták, P.

    2012-01-01

    Roč. 92, č. 1 (2012), s. 668-673 ISSN 0143-7208 R&D Projects: GA ČR GA203/09/0691 Institutional research plan: CEZ:AV0Z40320502 Keywords : calix[4]arene * tetrathiafulvalene * anion recognition * receptor * NMR titration * UV/vis spectroscopy Subject RIV: CA - Inorganic Chemistry Impact factor: 3.532, year: 2012

  11. 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....

  12. 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)...

  13. 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...

  14. Incorporating TCNQ into thiophene-fused heptacene for n-channel field effect transistor

    KAUST Repository

    Ye, Qun

    2012-06-01

    Incorporation of electron-deficient tetracyanoquinodimethane (TCNQ) into electron-rich thiophene-fused heptacene was successfully achieved for the purpose of stabilizing longer acenes and generating new n-type organic semiconductors. The heptacene-TCNQ derivative 1 was found to have good stability and an expected electron transporting property. Electron mobility up to 0.01 cm 2 V -1 s -1 has been obtained for this novel material in solution processed organic field effect transistors. © 2012 American Chemical Society.

  15. Bottom-up on-crystal in-chip formation of a conducting salt and a view of its restructuring: From organic insulator to conducting >switch> through microfluidic manipulation

    OpenAIRE

    Puigmartí-Luis, Josep; Paradinas, Markos; Bailo, Elena; Rodríguez-Trujillo, Romen; Pfattner, Raphael; Ocal, Carmen; Amabilino, David B.

    2015-01-01

    The chemical modification of an immobilized single crystal in a fluid cell is reported, whereby a material with switching functions is generated in situ by generating a chemical reagent in the flow. Crystals of the insulating organic crystal of TCNQ (tetracyanoquinodimethane) were grown in a microfluidic channel and were trapped using a pneumatic valve, a nascent technique for materials manipulation. They were subsequently reduced using solution-deposited silver to provide a conducting materi...

  16. Organic superconductors: A current overview, synthesis, structure and theory

    International Nuclear Information System (INIS)

    Wang, H.H.; Beno, M.A.; Carlson, K.D.; Geiser, U.; Kini, A.M.; Williams, J.M.

    1990-01-01

    To date, four types of crystal packing motifs (β, θ, κ and α) are known to lead to superconductivity in the BEDT-TTF based materials, where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene. The syntheses, crystal structures, physical properties and band electronic structures of these materials will be reviewed. Recent progress made in the oxygen containing analogue, BEDO-TTF [bis(ethylenedioxo)tetrathiofulvalene] will be presented. The implication and future prospect of organic superconductors will be discussed

  17. Electrochromism for organic materials in polymeric all-solid-state systems

    Science.gov (United States)

    Hirai, Yoshihiko; Tani, Chizuka

    1983-10-01

    This letter reports a new electrochromic polymeric film system consisting of a polymer, an electrochromic (EC) dye which is pyrazoline or tetrathiafulvalene (TTF), and lithium perchlorate (LiClO4). The electrochromic cell structure is glass/ITO/polymeric EC film/Au film. The cell using pyrazoline as an EC dye exhibited yellow coloration at 1.0 V and the cell with TTF exhibited red coloration at 3.5 V. These cells exhibited memory.

  18. Halides of BET-TTF: novel hydrated molecular metals

    Energy Technology Data Exchange (ETDEWEB)

    Laukhina, E.; Ribera, E.; Vidal-Gancedo, J.; Canadell, E.; Veciana, J.; Rovira, C. [Universidad Autonoma de Barcelona, Bellaterra (Spain). Inst. de Ciencia de Materials; Khasanov, S.; Zorina, L.; Shibaeva, R. [Rossijskaya Akademiya Nauk, Chernogolovka (Russian Federation). Inst. Fiziki Tverdogo Tela; Laukhin, V. [Inst. of Problems of Chemical Physics, RAS, Chernogolovka (Russian Federation); Honold, M.; Nam, M.-S.; Singleton, J. [Clarendon Lab., Univ. of Oxford (United Kingdom)

    2000-01-07

    A hint of superconducting transition has been observed for the first time in a cation radical salt derived from bisethylenethio-tetrathiafulvalene (BET-TTF), the salt (BET-TTF){sub 2}Br.3H{sub 2}O. Here the synthesis, X-ray structure, and physical properties of two hydrated halides of BET-TTF that are isostructural and present stable metallic properties are described. (orig.)

  19. 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.

  20. Very Strong Binding for a Neutral Calix[4]pyrrole Receptor Displaying Positive Allosteric Binding

    DEFF Research Database (Denmark)

    Duedal, Troels; Nielsen, Kent; Olsen, Gunnar

    2017-01-01

    . The tetrathiafulvalene (TTF) subunits in the tetraTTF-calix[4]pyrrole receptor 1 present a nearly perfect shape and electronic complementarity to the NTCDA guest, which was confirmed by X-ray crystal structure analysis, DFT calculations, and electron density surface mapping. The complexation results in formation...... of a charge transfer complex (22⊆1), that is visualized as a color change from yellow to brown....

  1. Increased electronic coupling in silicon nanocrystal networks doped with F4-TCNQ.

    Science.gov (United States)

    Carvalho, Alexandra; Oberg, Sven; Rayson, Mark J; Briddon, Patrick R

    2013-02-01

    The modification of the electronic structure of silicon nanocrystals using an organic dopant, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), is investigated using first-principles calculations. It is shown that physisorbed F4-TCNQ molecules have the effect of oxidizing the nanocrystal, attracting the charge density towards the F4-TCNQ-nanocrystal interface, and decreasing the excitation energy of the system. In periodic F4-TCNQ/nanocrystal superlattices, F4-TCNQ is suggested to enhance exciton separation, and in the presence of free holes, to serve as a bridge for electron/hole transfer between adjacent nanocrystals.

  2. Atomic force microscopy investigation of growth process of organic TCNQ aggregates on SiO2 and mica substrates

    Science.gov (United States)

    Huan, Qing; Hu, Hao; Pan, Li-Da; Xiao, Jiang; Du, Shi-Xuan; Gao, Hong-Jun

    2010-08-01

    Deposition patterns of tetracyanoquinodimethane (TCNQ) molecules on different surfaces are investigated by atomic force microscopy. A homemade physical vapour deposition system allows the better control of molecule deposition. Taking advantage of this system, we investigate TCNQ thin film growth on both SiO2 and mica surfaces. It is found that dense island patterns form at a high deposition rate, and a unique seahorse-like pattern forms at a low deposition rate. Growth patterns on different substrates suggest that the fractal pattern formation is dominated by molecule-molecule interaction. Finally, a phenomenal “two-branch" model is proposed to simulate the growth process of the seahorse pattern.

  3. Atomic force microscopy investigation of growth process of organic TCNQ aggregates on SiO2 and mica substrates

    International Nuclear Information System (INIS)

    Qing, Huan; Hao, Hu; Li-Da, Pan; Jiang, Xiao; Shi-Xuan, Du; Hong-Jun, Gao

    2010-01-01

    Deposition patterns of tetracyanoquinodimethane (TCNQ) molecules on different surfaces are investigated by atomic force microscopy. A homemade physical vapour deposition system allows the better control of molecule deposition. Taking advantage of this system, we investigate TCNQ thin film growth on both SiO 2 and mica surfaces. It is found that dense island patterns form at a high deposition rate, and a unique seahorse-like pattern forms at a low deposition rate. Growth patterns on different substrates suggest that the fractal pattern formation is dominated by molecule–molecule interaction. Finally, a phenomenal “two-branch” model is proposed to simulate the growth process of the seahorse pattern. (general)

  4. TCNQ-embedded heptacene and nonacene: Synthesis, characterization and physical properties

    KAUST Repository

    Ye, Qun

    2013-01-01

    Incorporation of 7,7,8,8-tetracyanoquinodimethane (TCNQ) moieties into the acene backbone has been successfully achieved and two heptacene-TCNQ derivatives and one nonacene-TCNQ derivative have been synthesized and well characterized. Two TCNQ moieties have been embedded into heptacene and nonacene backbones for the first time. All the three compounds have good stability and solubility due to the presence of TCNQ moieties. Single crystal analysis revealed a bent butterfly-like conformation of these molecules. Their charge transport properties have been characterized using organic field effect transistors (OFETs). © 2013 The Royal Society of Chemistry.

  5. Measurement of the ground-state distributions in bistable mechanically interlocked molecules using slow scan rate cyclic voltammetry.

    Science.gov (United States)

    Fahrenbach, Albert C; Barnes, Jonathan C; Li, Hao; Benítez, Diego; Basuray, Ashish N; Fang, Lei; Sue, Chi-Hau; Barin, Gokhan; Dey, Sanjeev K; Goddard, William A; Stoddart, J Fraser

    2011-12-20

    In donor-acceptor mechanically interlocked molecules that exhibit bistability, the relative populations of the translational isomers--present, for example, in a bistable [2]rotaxane, as well as in a couple of bistable [2]catenanes of the donor-acceptor vintage--can be elucidated by slow scan rate cyclic voltammetry. The practice of transitioning from a fast scan rate regime to a slow one permits the measurement of an intermediate redox couple that is a function of the equilibrium that exists between the two translational isomers in the case of all three mechanically interlocked molecules investigated. These intermediate redox potentials can be used to calculate the ground-state distribution constants, K. Whereas, (i) in the case of the bistable [2]rotaxane, composed of a dumbbell component containing π-electron-rich tetrathiafulvalene and dioxynaphthalene recognition sites for the ring component (namely, a tetracationic cyclophane, containing two π-electron-deficient bipyridinium units), a value for K of 10 ± 2 is calculated, (ii) in the case of the two bistable [2]catenanes--one containing a crown ether with tetrathiafulvalene and dioxynaphthalene recognition sites for the tetracationic cyclophane, and the other, tetrathiafulvalene and butadiyne recognition sites--the values for K are orders (one and three, respectively) of magnitude greater. This observation, which has also been probed by theoretical calculations, supports the hypothesis that the extra stability of one translational isomer over the other is because of the influence of the enforced side-on donor-acceptor interactions brought about by both π-electron-rich recognition sites being part of a macrocyclic polyether.

  6. Electronic processes in TTF-derived complexes studied by IR spectroscopy

    Science.gov (United States)

    Graja, Andrzej

    2001-09-01

    We focus our attention on the plasma-edge-like dispersion of the reflectance spectra of the selected bis(ethylenodithio)tetrathiafulvalene (BEDT-TTF)-derived organic conductors. The standard procedure to determine the electron transport parameters in low-dimensional organic conductors consists of fitting the appropriate theoretical models with the experimental reflectance data. This procedure provides us with basic information like plasma frequency, the optical effective mass of charge carriers, their number, mean free path and damping constant. Therefore, it is concluded that the spectroscopy is a powerful tool to study the electronic processes in conducting organic solids.

  7. Vortex-pair nucleation at defects: A mechanism for anomalous temperature dependence in the superconducting screening length

    International Nuclear Information System (INIS)

    Hebard, A.F.; Fiory, A.T.; Siegal, M.P.; Phillips, J.M.; Haddon, R.C.

    1991-01-01

    Low-field ac screening measurements on YBa 2 Cu 3 O 7-δ films and (BEDT-TTF) 2 Cu(SCN) 2 crystals [where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene], both thought to contain a high density of defects, reveal a diminution of screening and a common extrinsic temperature dependence of the screening length λ. Vortex-core pinning at the defects is shown to give a low-temperature T 2 power-law temperature dependence to λ that, in contrast to the exponential behavior expected from s-wave pairing, can be mistaken as evidence for lines or nodes of the energy gap on the Fermi surface

  8. Synthesis and characterization of the cyanobenzene-ethylenedithio-TTF donor

    Directory of Open Access Journals (Sweden)

    Sandrina Oliveira

    2015-06-01

    Full Text Available A dissymmetric TTF-type electron donor, cyanobenzene-ethylenedithio-tetrathiafulvalene (CNB-EDT-TTF, was obtained in high yield, by a cross-coupling reaction with triethyl phosphite between 2-thioxobenzo[d][1,3]dithiole-5-carbonitrile and 5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-one. This new donor was characterized namely by single crystal X-ray diffraction, cyclic voltammetry, NMR, UV-visible and IR spectroscopy.

  9. Metallic conductivity in a disordered charge-transfer salt derived from cis-BET-TTF

    Energy Technology Data Exchange (ETDEWEB)

    Rovira, C. [Inst. de Ciencia de Materials de Barcelona (CSIC) (Spain); Tarres, J. [Inst. de Ciencia de Materials de Barcelona (CSIC) (Spain); Ribera, E. [Inst. de Ciencia de Materials de Barcelona (CSIC) (Spain); Veciana, J. [Inst. de Ciencia de Materials de Barcelona (CSIC) (Spain); Canadell, E. [Inst. de Ciencia de Materials de Barcelona (CSIC) (Spain); Molins, E. [Inst. de Ciencia de Materials de Barcelona (CSIC) (Spain); Mas, M. [Inst. de Ciencia de Materials de Barcelona (CSIC) (Spain); Laukhin, V. [Inst. de Ciencia de Materials de Barcelona (CSIC) (Spain)]|[Rossijskaya Akademiya Nauk, Chernogolovka (Russian Federation). Inst. Khimicheskoj Fiziki; Doublet, M.L. [Lab. de Structure et Dynamique (CNRS), Univ. de Montpellier 2 (France); Cowan, D.O. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry; Yang, S. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry

    1997-02-28

    The first example of a metallic charge-transfer salt derived from cis-bis(ethylenethio)-tetrathiafulvalene (BET-TTF) is reported. (BET-TTF){sub 2}SCN and (BET-TTF)SCN salts were obtained by electrocrystallization starting from trans-BET-TTF. X-ray crystal structure of the mixed-valence salt revealed that trans-cis isomerization occurs upon one electron oxidation. In spite of the structural disorder in both BET-TTF and the counterion, 2:1 salt is metallic down to 60 K and then resistance increases slowly down to 4 K. (orig.)

  10. Substituent effects on the electron affinities and ionization energies of tria-, penta-, and heptafulvenes: a computational investigation

    DEFF Research Database (Denmark)

    Dahlstrand, Christian; Yamazaki, Kaoru; Kilså, Kristine

    2010-01-01

    (TCNQ) and tetrathiafulvalene (TTF) as representing strong electron-acceptor and -donor compounds, respectively. The substituents X at the exocyclic positions of the fulvenes were either NH(2), H, or CN, while the substituents Y at the ring positions were H, Cl, F, CN, or NH(2). The variations...... of bis(fulvene)s, i.e., compounds composed of a donor-type heptafulvene fused with an acceptor-type pentafulvene, and it was revealed that these bis(fulvene)s can be designed so that the IE and EA of the two separate fulvene segments are retained, potentially allowing for the design of compact donor...

  11. 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...

  12. Organic molecules deposited on graphene: A computational investigation of self-assembly and electronic structure

    International Nuclear Information System (INIS)

    Oliveira, I. S. S. de; Miwa, R. H.

    2015-01-01

    We use ab initio simulations to investigate the adsorption and the self-assembly processes of tetracyanoquinodimethane (TCNQ), tetrafluoro-tetracyanoquinodimethane (F4-TCNQ), and tetrasodium 1,3,6,8-pyrenetetrasulfonic acid (TPA) on the graphene surface. We find that there are no chemical bonds at the molecule–graphene interface, even at the presence of grain boundaries on the graphene surface. The molecules bond to graphene through van der Waals interactions. In addition to the molecule–graphene interaction, we performed a detailed study of the role played by the (lateral) molecule–molecule interaction in the formation of the, experimentally verified, self-assembled layers of TCNQ and TPA on graphene. Regarding the electronic properties, we calculate the electronic charge transfer from the graphene sheet to the TCNQ and F4-TCNQ molecules, leading to a p-doping of graphene. Meanwhile, such charge transfer is reduced by an order of magnitude for TPA molecules on graphene. In this case, it is not expected a significant doping process upon the formation of self-assembled layer of TPA molecules on the graphene sheet

  13. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali; Khashab, Niveen M.; Fahrenbach, Albert C.; Friedman, Douglas C.; Colvin, Michael T.; Coti, Karla K.; Bení tez, Diego S.; Tkatchouk, Ekaterina; Olsen, John Carl; Belowich, Matthew E.; Carmieli, Raanan; Khatib, Hussam A.; Goddard, William Andrew III; Wasielewski, Michael R.; Stoddart, Fraser Fraser Raser

    2009-01-01

    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.

  14. 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.

  15. Cu diffusion as an alternative method for nanopatterned CuTCNQ film growth

    International Nuclear Information System (INIS)

    Capitán, M J; Álvarez, J; Miranda, R; Navío, C

    2016-01-01

    In this paper we show by means of ‘in situ’ x-ray diffraction studies that CuTCNQ formation from Cu(solid)–TCNQ(solid tetracyanoquinodimethane) goes through Cu diffusion at room temperature. The film quality depends on the TCNQ evaporation rate. At low evaporation rate we get a single phase-I CuTCNQ film very well crystallized and well oriented. The film has a CuTCNQ(0 2 0) orientation. The film is formed by CuTCNQ nanorods of a very homogeneous size. The film homogeneity has also been seen by atomic force microscopy (AFM). The electronic properties of the film have been measured by x-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS). Thus, the Cu-diffusion method has arisen as a very simple, clean and efficient method to grow localized CuTCNQ nanorods on Cu, opening up new insights for technological applications. (paper)

  16. Switching behaviour of individual Ag-TCNQ nanowires: an in situ transmission electron microscopy study

    Science.gov (United States)

    Ran, Ke; Rösner, Benedikt; Butz, Benjamin; Fink, Rainer H.; Spiecker, Erdmann

    2016-10-01

    The organic semiconductor silver-tetracyanoquinodimethane (Ag-TCNQ) exhibits electrical switching and memory characteristics. Employing a scanning tunnelling microscopy setup inside a transmission electron microscope, the switching behaviour of individual Ag-TCNQ nanowires (NWs) is investigated in detail. For a large number of NWs, the switching between a high (OFF) and a low (ON) resistance state was successfully stimulated by negative bias sweeps. Fitting the experimental I-V curves with a Schottky emission function makes the switching features prominent and thus enables a direct evaluation of the switching process. A memory cycle including writing, reading and erasing features is demonstrated at an individual NW. Moreover, electronic failure mechanisms due to Joule heating are discussed. These findings have a significant impact on our understanding of the switching behaviour of Ag-TCNQ.

  17. Magnetic ordering in TCNQ-based metal–organic frameworks with host–guest interactions

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xuan; Saber, Mohamed R.; Prosvirin, Andrey P.; Reibenspies, Joseph H.; Sun, Lei; Ballesteros-Rivas, Maria; Zhao, Hanhua; Dunbar, Kim R. (MIT); (TAM)

    2015-09-03

    Host–guest interactions between the aromatic molecules benzene, toluene, aniline and nitrobenzene and the redox-active TCNQ-based metal–organic framework (MOF), Fe(TCNQ)(4,4'-bpy) (1) (TCNQ = 7,7,8,8-tetracyanoquinodimethane), have been found to modulate spontaneous magnetization behaviours at low temperatures. An analogous MOF, Mn(TCNQ)(4,4'-bpy) (2) with isotropic Mn(II) ions as well as the two-dimensional compound Fe(TCNQ)(DMF)2·2DMF (3·2DMF), were also prepared as models for studying the effects of single-ion magnetic anisotropy and structural distortion on spin canting. The results indicate guest-dependent long range magnetic ordering occurs at low temperatures, which correlates with the electrostatic and steric effects of the incorporated aromatic guests.

  18. An Electrically Switchable Metal-Organic Framework

    Science.gov (United States)

    Fernandez, Carlos A.; Martin, Paul C.; Schaef, Todd; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-08-01

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  19. Structural origination of charge transfer complex nanostructures: Excellent candidate for field emission

    International Nuclear Information System (INIS)

    Pal, Shreyasi; Chattopadhyay, Kalyan Kumar

    2016-01-01

    Worldwide strategies for amalgamating rationally controlled one-dimensional organic nanowires are of fundamental importance for their applications in flexible, cheaper and lighter electronics. In this work we have fabricated large-area, ordered CuTCNQ (copper-7,7,8,8-tetracyanoquinodimethane) nano architecture arrays over flexible conducting substrate and discussed the rational growth and integration of nanostructures. Here we adopted the organic solid phase reaction (VLS) technique for the growth of organic hierarchies and investigated how field emission properties changes by tuning the nanostructures morphology i.e., by varying length, diameter, alignment and orientation over flexible substrate. The CuTCNQ nanowires with optimized geometry exhibit excellent high field emission performance with low turn-on and threshold field values. The result strongly indicate that CuTCNQ nanowires on flexible carbon cloth substrate are promising candidates for constructing cold cathode based emission display devices, vacuum nanoelectronics, and etc.

  20. Microscopic properties of ionic liquid/organic semiconductor interfaces revealed by molecular dynamics simulations.

    Science.gov (United States)

    Yokota, Yasuyuki; Miyamoto, Hiroo; Imanishi, Akihito; Takeya, Jun; Inagaki, Kouji; Morikawa, Yoshitada; Fukui, Ken-Ichi

    2018-05-09

    Electric double-layer transistors based on ionic liquid/organic semiconductor interfaces have been extensively studied during the past decade because of their high carrier densities at low operation voltages. Microscopic structures and the dynamics of ionic liquids likely determine the device performance; however, knowledge of these is limited by a lack of appropriate experimental tools. In this study, we investigated ionic liquid/organic semiconductor interfaces using molecular dynamics to reveal the microscopic properties of ionic liquids. The organic semiconductors include pentacene, rubrene, fullerene, and 7,7,8,8-tetracyanoquinodimethane (TCNQ). While ionic liquids close to the substrate always form the specific layered structures, the surface properties of organic semiconductors drastically alter the ionic dynamics. Ionic liquids at the fullerene interface behave as a two-dimensional ionic crystal because of the energy gain derived from the favorable electrostatic interaction on the corrugated periodic substrate.

  1. Structural origination of charge transfer complex nanostructures: Excellent candidate for field emission

    Energy Technology Data Exchange (ETDEWEB)

    Pal, Shreyasi; Chattopadhyay, Kalyan Kumar [Thin Films and Nanoscience Laboratory, Department of Physics, Jadavpur University, Kolkata 700032 (India)

    2016-05-23

    Worldwide strategies for amalgamating rationally controlled one-dimensional organic nanowires are of fundamental importance for their applications in flexible, cheaper and lighter electronics. In this work we have fabricated large-area, ordered CuTCNQ (copper-7,7,8,8-tetracyanoquinodimethane) nano architecture arrays over flexible conducting substrate and discussed the rational growth and integration of nanostructures. Here we adopted the organic solid phase reaction (VLS) technique for the growth of organic hierarchies and investigated how field emission properties changes by tuning the nanostructures morphology i.e., by varying length, diameter, alignment and orientation over flexible substrate. The CuTCNQ nanowires with optimized geometry exhibit excellent high field emission performance with low turn-on and threshold field values. The result strongly indicate that CuTCNQ nanowires on flexible carbon cloth substrate are promising candidates for constructing cold cathode based emission display devices, vacuum nanoelectronics, and etc.

  2. Crystal growth of new charge-transfer salts based on π-conjugated donor molecules

    Energy Technology Data Exchange (ETDEWEB)

    Morherr, Antonia, E-mail: morherr@stud.uni-frankfurt.de [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Witt, Sebastian [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Chernenkaya, Alisa [Graduate School Materials Science in Mainz, 55128 Mainz (Germany); Institut für Physik, Johannes Gutenberg-Universität, 55099 Mainz (Germany); Bäcker, Jan-Peter [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Schönhense, Gerd [Institut für Physik, Johannes Gutenberg-Universität, 55099 Mainz (Germany); Bolte, Michael [Institut für anorganische Chemie, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Krellner, Cornelius [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany)

    2016-09-01

    New charge transfer crystals of π-conjugated, aromatic molecules (phenanthrene and picene) as donors were obtained by physical vapor transport. The melting behavior, optimization of crystal growth and the crystal structure are reported for charge transfer salts with (fluorinated) tetracyanoquinodimethane (TCNQ-F{sub x}, x=0, 2, 4), which was used as acceptor material. The crystal structures were determined by single-crystal X-ray diffraction. Growth conditions for different vapor pressures in closed ampules were applied and the effect of these starting conditions for crystal size and quality is reported. The process of charge transfer was investigated by geometrical analysis of the crystal structure and by infrared spectroscopy on single crystals. With these three different acceptor strengths and the two sets of donor materials, it is possible to investigate the distribution of the charge transfer systematically. This helps to understand the charge transfer process in this class of materials with π-conjugated donor molecules.

  3. Ultrafast exciton decay in PbS quantum dots through simultaneous electron and hole recombination with a surface-localized ion pair

    Energy Technology Data Exchange (ETDEWEB)

    Edme, Kedy; Bettis Homan, Stephanie; Nepomnyashchii, Alexander B.; Weiss, Emily A., E-mail: e-weiss@northwestern.edu

    2016-06-01

    Highlights: • We synthesize complexes of PbS quantum dots (QDs) and tetracyanoquinodimethane (TCNQ). Each PbS QD spontaneously reduces up to 17 TCNQ molecules. • The photoluminescence of the PbS QDs is quenched in the presence of the reduced TCNQ species through ultrafast non-radiative, simultaneous decay of the electron and hole. • We assign this decay to a four-carrier, concerted charge recombination mechanism with the surface localized sulfur–TCNQ{sup x−} ion pair. - Abstract: This paper describes the ultrafast decay of the band-edge exciton in PbS quantum dots (QDs) through simultaneous recombination of the excitonic hole and electron with the surface localized ion pair formed upon adsorption of tetracyanoquinodimethane (TCNQ). Each PbS QD (R = 1.8 nm) spontaneously reduces up to 17 TCNQ molecules upon adsorption of the TCNQ molecule to a sulfur on the QD surface. The photoluminescence of the PbS QDs is quenched in the presence of the reduced TCNQ species through ultrafast (⩽15-ps) non-radiative decay of the exciton; the rate constant for the decay process increases approximately linearly with the number of adsorbed, reduced TCNQ molecules. Near-infrared and mid-infrared transient absorption show that this decay occurs through simultaneous transfer of the excitonic electron and hole, and is assigned to a four-carrier, concerted charge recombination mechanism based on the observations that (i) the PL of the QDs recovers when spontaneously reduced TCNQ{sup 1−} desorbs from the QD surface upon addition of salt, and (ii) the PL of the QDs is preserved when another spontaneous oxidant, ferrocinium, which cannot participate in charge transfer in its reduced state, is substituted for TCNQ.

  4. Diels-Alder cyclo-addition as an efficient tool for linking π-donors onto fullerene C60

    International Nuclear Information System (INIS)

    Hudhomme, P.

    2006-01-01

    Diels-Alder reaction of endo-cyclic, acyclic 1,3-dienes or (hetero) o-quinodimethanes with the dienophilic fullerene C 60 is presented as an efficient tool for linking electro-active units giving rise to systems where both the donor and C 60 partners take up well defined volumes and orientations with respect to one another. While porphyrin is the most frequently used electron donor in artificial photosynthetic models, C 60 -based tetrathiafulvalene (TTF) or p-conjugated oligomer adducts remain interesting candidates for the preparation of photovoltaic devices. In this account, we focus on the use of the Diels-Alder cyclo-addition and its use in the synthesis of TTF-C 60 dyads, (TTF) n -C 60 polyads and C 60 -TTF-C 60 dumbbells as part of ongoing research into materials which display efficient photo-induced electron transfer. (author)

  5. Controlling the Host-Guest Interaction Mode through a Redox Stimulus.

    Science.gov (United States)

    Szalóki, György; Croué, Vincent; Carré, Vincent; Aubriet, Frédéric; Alévêque, Olivier; Levillain, Eric; Allain, Magali; Aragó, Juan; Ortí, Enrique; Goeb, Sébastien; Sallé, Marc

    2017-12-18

    A proof-of-concept related to the redox-control of the binding/releasing process in a host-guest system is achieved by designing a neutral and robust Pt-based redox-active metallacage involving two extended-tetrathiafulvalene (exTTF) ligands. When neutral, the cage is able to bind a planar polyaromatic guest (coronene). Remarkably, the chemical or electrochemical oxidation of the host-guest complex leads to the reversible expulsion of the guest outside the cavity, which is assigned to a drastic change of the host-guest interaction mode, illustrating the key role of counteranions along the exchange process. The reversible process is supported by various experimental data ( 1 H NMR spectroscopy, ESI-FTICR, and spectroelectrochemistry) as well as by in-depth theoretical calculations performed at the density functional theory (DFT) level. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  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......) are chemically merged together to form cruciform-like structures that are an essential part of the thesis. The cruciform molecules were subjected to molecular conductance measurements to explore their capability towards single-crystal field-effect transistors (Part 1), molecular wires, and single electron......, however, was obtained by a study of a single molecular transistor. The investigated OPE5-TTF compound was captured in a three-terminal experiment, whereby manipulation of the molecule’s electronic spin was possible in different charge states. Thus, we demonstrated how the cruciform molecules could...

  7. 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...... and decreases again as the second redox process is passed. This is described as an “off–on–off–on–off” conductance switching behavior. This molecular conductance vs electrochemical potential relation could be modeled well as a sequential two-step charge transfer process with full or partial vibrational...

  8. Isolation by crystallization of translational isomers of a bistable donor-acceptor [2]catenane

    Science.gov (United States)

    Wang, Cheng; Olson, Mark A.; Fang, Lei; Benítez, Diego; Tkatchouk, Ekaterina; Basu, Subhadeep; Basuray, Ashish N.; Zhang, Deqing; Zhu, Daoben; Goddard, William A.; Stoddart, J. Fraser

    2010-01-01

    The template-directed synthesis of a bistable donor-acceptor [2]catenane wherein both translational isomers—one in which a tetrathiafulvalene unit in a mechanically interlocked crown ether occupies the cavity of a cyclobis(paraquat-p-phenylene) ring and the other in which a 1,5-dioxynaphthalene unit in the crown ether resides inside the cavity of the tetracationic cyclophane—exist in equilibrium in solution, has led to the isolation and separation by hand picking of single crystals colored red and green, respectively. These two crystalline co-conformations have been characterized separately at both the molecular and supramolecular levels, and also by dynamic NMR spectroscopy in solution where there is compelling evidence that the mechanically interlocked molecules are present as a complex mixture of translational, configurational, and conformational isomers wherein the isomerization is best described as being a highly dynamic and adaptable phenomenon. PMID:20663950

  9. 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.

  10. 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.

  11. Molecular materials for organic field-effect transistors

    International Nuclear Information System (INIS)

    Mori, T

    2008-01-01

    Organic field-effect transistors are important applications of thin films of molecular materials. A variety of materials have been explored for improving the performance of organic transistors. The materials are conventionally classified as p-channel and n-channel, but not only the performance but also even the carrier polarity is greatly dependent on the combinations of organic semiconductors and electrode materials. In this review, particular emphasis is laid on multi-sulfur compounds such as tetrathiafulvalenes and metal dithiolates. These compounds are components of highly conducting materials such as organic superconductors, but are also used in organic transistors. The charge-transfer complexes are used in organic transistors as active layers as well as electrodes. (topical review)

  12. Enzymatic biofuel cell based on electrodes modified with lipid liquid-crystalline cubic phases

    Science.gov (United States)

    Nazaruk, Ewa; Smoliński, Sławomir; Swatko-Ossor, Marta; Ginalska, Grażyna; Fiedurek, Jan; Rogalski, Jerzy; Bilewicz, Renata

    Two glassy carbon electrodes modified with enzymes embedded in lyotropic liquid-crystalline cubic phase were used for the biofuel cell construction. The monoolein liquid-crystalline film allowed to avoid separators in the biofuel cell. Glucose and oxygen as fuels, and glucose oxidase and laccase as anode and cathode biocatalysts, respectively were used. The biofuel cell parameters were examined in McIlvaine buffer, pH 7 solution containing 15 mM of glucose and saturated with dioxygen. A series of mediators were tested taking into account their formal potentials, stability in the cubic phase and efficiency of mediation. Most stable was the biofuel cell based on tetrathiafulvalene (TTF) and 2,2‧-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as anode and cathode mediators, respectively. The open-circuit voltage was equal to 450 ± 40 mV. The power densities and current densities were measured for all the systems studied.

  13. TCNQ-induced in-situ electrochemical deposition for the synthesis of silver nanodendrites as efficient bifunctional electrocatalysts

    International Nuclear Information System (INIS)

    Chen, Zhengyan; Li, Congling; Ni, Yangyang; Kong, Fantao; Zhang, Yongbo; Kong, Aiguo; Shan, Yongkui

    2017-01-01

    Graphical abstract: Silver nanodendrites with superior electrocatalytic activity for oxygen reduction reaction (ORR) and hydrogen peroxide detection were synthesized by electrodeposition method using organic semiconductor 7,7,8,8-tetracyanoquinodimethane (TCNQ) as the inducer. - Highlights: • AgNDs were obtained by electrodepositing route under the induction of TCNQ. • The AgNDs-TCNQ/GCE showed superior activity comparable to Pt/C for ORR. • The AgNDs-TCNQ/GCE exhibited highly catalytic activity toward H_2O_2 detection. • A novel pathway for synthesizing bifunctional Ag-based electrocatalyst. - Abstract: Sliver (Ag) nanodendrites (AgNDs) directly growing on the glassy carbon electrode (GCE) were obtained by an in-situ electrodepositing route under the induction of organic semiconductor 7,7,8,8-tetracyanoquinodimethane (TCNQ). The morphology of the Ag nanostructures can be controlled by the electrodepositing time, applied potentials, and the concentrations of Ag ions. The AgNDs/TCNQ/GCE obtained at the optimized conditions displays the oxygen reduction reaction (ORR) onset potential of 0.98 V, which is the same as that over Pt/C-JM catalyst (0.98 V). It demonstrated that AgNDs possessed the highest electrocatalytic activity for ORR among the various Ag-based electrocatalysts reported in literature in alkaline electrolyte. At the same time, the performance of AgNDs/TCNQ/GCE toward hydrogen peroxide detection was investigated in a range of the concentration from 10 μM to 17 mM. It also showed the higher catalytic activity for hydrogen peroxide reduction reaction with the hydrogen peroxide detection limit reaching 0.47 μM level. The Tafel polarization curve, electrochemically active surface area, and the electrochemical impedance were measured to understand and explore the catalytic behavior of the prepared AgNDs/TCNQ/GCE. The enhanced performance of AgNDs for ORR and hydrogen peroxide detection can be ascribed to the special tree-like morphology with highly

  14. Experimental and numerical investigation of contact-area-limited doping for top-contact pentacene thin-film transistors with Schottky contact.

    Science.gov (United States)

    Noda, Kei; Wada, Yasuo; Toyabe, Toru

    2015-10-28

    Effects of contact-area-limited doping for pentacene thin-film transistors with a bottom-gate, top-contact configuration were investigated. The increase in the drain current and the effective field-effect mobility was achieved by preparing hole-doped layers underneath the gold contact electrodes by coevaporation of pentacene and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), confirmed by using a thin-film organic transistor advanced simulator (TOTAS) incorporating Schottky contact with a thermionic field emission (TFE) model. Although the simulated electrical characteristics fit the experimental results well only in the linear regime of the transistor operation, the barrier height for hole injection and the gate-voltage-dependent hole mobility in the pentacene transistors were evaluated with the aid of the device simulation. This experimental data analysis with the simulation indicates that the highly-doped semiconducting layers prepared in the contact regions can enhance the charge carrier injection into the active semiconductor layer and concurrent trap filling in the transistor channel, caused by the mitigation of a Schottky energy barrier. This study suggests that both the contact-area-limited doping and the device simulation dealing with Schottky contact are indispensable in designing and developing high-performance organic thin-film transistors.

  15. Organic nanowire hierarchy over fabric platform for flexible cold cathode

    Science.gov (United States)

    Maiti, Soumen; Narayan Maiti, Uday; Pal, Shreyasi; Chattopadhyay, Kalyan Kumar

    2013-11-01

    Organic charge transfer (CT) complexes initiated a growing interest in modern electronic devices owing to their easy processability and unique characteristics. In this work, three-dimensional field emitters comprising metal-organic charge transfer complex nanostructures of AgTCNQ and CuTCNQ (TCNQ, 7,7,8,8-tetracyanoquinodimethane) over flexible fabric substrate are realized. Deliberate control over the reaction parameter during organic solid phase reaction leads to modification in structural parameters of the nanowires (i.e. length, diameter) as well as their arrangement atop the carbon fibers. The optimized arrays of AgTCNQ and CuTCNQ nanowires exhibit excellent field electron emission performance with very low turn-on (1.72 and 2.56 V μm-1) and threshold fields (4.21 and 6.33 V μm-1) respectively, which are comparable to those of the best organic field emitters reported to date. The underlying conducting carbon cloth with special woven-like geometry not only offers a flexible platform for nanowire growth, but also provides an additional field enhancement to ease the electron emission.

  16. Organic nanowire hierarchy over fabric platform for flexible cold cathode

    International Nuclear Information System (INIS)

    Maiti, Soumen; Pal, Shreyasi; Chattopadhyay, Kalyan Kumar; Maiti, Uday Narayan

    2013-01-01

    Organic charge transfer (CT) complexes initiated a growing interest in modern electronic devices owing to their easy processability and unique characteristics. In this work, three-dimensional field emitters comprising metal–organic charge transfer complex nanostructures of AgTCNQ and CuTCNQ (TCNQ, 7,7,8,8-tetracyanoquinodimethane) over flexible fabric substrate are realized. Deliberate control over the reaction parameter during organic solid phase reaction leads to modification in structural parameters of the nanowires (i.e. length, diameter) as well as their arrangement atop the carbon fibers. The optimized arrays of AgTCNQ and CuTCNQ nanowires exhibit excellent field electron emission performance with very low turn-on (1.72 and 2.56 V μm −1 ) and threshold fields (4.21 and 6.33 V μm −1 ) respectively, which are comparable to those of the best organic field emitters reported to date. The underlying conducting carbon cloth with special woven-like geometry not only offers a flexible platform for nanowire growth, but also provides an additional field enhancement to ease the electron emission. (paper)

  17. Development and Validation of Spectrophotometric Methods for the Determination of Rasagiline in Pharmaceutical Preparations

    Directory of Open Access Journals (Sweden)

    Serife Evrim Kepekci Tekkeli

    2013-01-01

    Full Text Available This study presents three simple, rapid, and accurate spectrophotometric methods for the determination of Rasagiline (RSG in pharmaceutical preparations. The determination procedures depend on the reaction of RSG with chloranilic acid for method A, tetrachloro-1,4-benzoquinone for method B, and 7,7,8,8-tetracyanoquinodimethane for method C. The colored products were quantitated spectrophotometrically at 524, 535, and 843 nm for methods A, B, and C, respectively. Different variables affecting the reaction were optimized. Linearity ranges of the methods with good correlation coefficients (0.9988–0.9996 were observed as 25–300 µg mL−1, 25–350 µg mL−1, and 50–500 µg mL−1 for methods A, B, and C, respectively. The formation of products takes place through different mechanisms. The sites of interaction were confirmed by elemental analysis using IR and 1H-NMR spectroscopy. The validation of the methods was carried out in terms of specificity, linearity, accuracy, precision, robustness, limit of detection, and limit of quantitation. No interference was observed from concomitants usually present in dosage forms. The methods were applied successfully to the determination of RSG in pharmaceutical preparations.

  18. Uniaxially oriented polycrystalline thin films and air-stable n-type transistors based on donor-acceptor semiconductor (diC8BTBT)(FnTCNQ) [n = 0, 2, 4

    Science.gov (United States)

    Shibata, Yosei; Tsutsumi, Jun'ya; Matsuoka, Satoshi; Matsubara, Koji; Yoshida, Yuji; Chikamatsu, Masayuki; Hasegawa, Tatsuo

    2015-04-01

    We report the fabrication of high quality thin films for semiconducting organic donor-acceptor charge-transfer (CT) compounds, (diC8BTBT)(FnTCNQ) (diC8BTBT = 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene and FnTCNQ [n = 0,2,4] = fluorinated derivatives of 7,7,8,8,-tetracyanoquinodimethane), which have a high degree of layered crystallinity. Single-phase and uniaxially oriented polycrystalline thin films of the compounds were obtained by co-evaporation of the component donor and acceptor molecules. Organic thin-film transistors (OTFTs) fabricated with the compound films exhibited n-type field-effect characteristics, showing a mobility of 6.9 × 10-2 cm2/V s, an on/off ratio of 106, a sub-threshold swing of 0.8 V/dec, and an excellent stability in air. We discuss the suitability of strong intermolecular donor-acceptor interaction and the narrow CT gap nature in compounds for stable n-type OTFT operation.

  19. Frequency Dependent Electrical and Dielectric Properties of Au/P3HT:PCBM:F4-TCNQ/n-Si Schottky Barrier Diode

    Science.gov (United States)

    Taşçıoğlu, İ.; Tüzün Özmen, Ö.; Şağban, H. M.; Yağlıoğlu, E.; Altındal, Ş.

    2017-04-01

    In this study, poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester: 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (P3HT:PCBM:F4-TCNQ) organic film was deposited on n-type silicon (n-Si) substrate by spin coating method. The electrical and dielectric analysis of Au/P3HT:PCBM:F4-TCNQ/n-Si Schottky barrier diode was conducted by means of capacitance-voltage ( C- V) and conductance-voltage ( G/ ω- V) measurements in the frequency range of 10 kHz-2 MHz. The C- V- f plots exhibit fairly large frequency dispersion due to excess capacitance caused by the presence of interface states ( N ss). The values of N ss located in semiconductor bandgap at the organic film/semiconductor interface were calculated by Hill-Coleman method. Experimental results show that dielectric constant ( ɛ') and dielectric loss ( ɛ″) decrease with increasing frequency, whereas loss tangent (tan δ) remains nearly the same. The decrease in ɛ' and ɛ″ was interpreted by the theory of dielectric relaxation due to interfacial polarization. It is also observed that ac electrical conductivity ( σ ac) and electric modulus ( M' and M″) increase with increasing frequency.

  20. Factors Governing Intercalation of Fullerenes and Other Small Molecules Between the Side Chains of Semiconducting Polymers Used in Solar Cells

    KAUST Repository

    Miller, Nichole Cates

    2012-08-22

    While recent reports have established signifi cant miscibility in polymer:fullerene blends used in organic solar cells, little is actually known about why polymers and fullerenes mix and how their mixing can be controlled. Here, X-ray diffraction (XRD), differential scanning calorimetry (DSC), and molecular simulations are used to study mixing in a variety of polymer:molecule blends by systematically varying the polymer and smallmolecule properties. It is found that a variety of polymer:fullerene blends mix by forming bimolecular crystals provided there is suffi cient space between the polymer side chains to accommodate a fullerene. Polymer:tetrafl uoro-tetracyanoquinodimethane (F4-TCNQ) bimolecular crystals were also observed, although bimolecular crystals did not form in the other studied polymer:nonfullerene blends, including those with both conjugated and non-conjugated small molecules. DSC and molecular simulations demonstrate that strong polymer-fullerene interactions can exist, and the calculations point to van der Waals interactions as a signifi cant driving force for molecular mixing. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Usefulness of charge-transfer complexation for the assessment of sympathomimetic drugs: Spectroscopic properties of drug ephedrine hydrochloride complexed with some π-acceptors

    Science.gov (United States)

    Refat, Moamen S.; Ibrahim, Omar B.; Saad, Hosam A.; Adam, Abdel Majid A.

    2014-05-01

    Recently, ephedrine (Eph) assessment in food products, pharmaceutical formulations, human fluids of athletes and detection of drug toxicity and abuse, has gained a growing interest. To provide basic data that can be used to assessment of Eph quantitatively based on charge-transfer (CT) complexation, the CT complexes of Eph with 7‧,8,8‧-tetracyanoquinodimethane (TCNQ), dichlorodicyanobenzoquinone (DDQ), 1,3-dinitrobenzene (DNB) or tetrabromothiophene (TBT) were synthesized and spectroscopically investigated. The newly synthesized complexes have been characterized via elemental analysis, IR, Raman, 1H NMR, and UV-visible spectroscopy. The formation constant (KCT), molar extinction coefficient (εCT) and other spectroscopic data have been determined using the Benesi-Hildebrand method and its modifications. The sharp, well-defined Bragg reflections at specific 2θ angles have been identified from the powder X-ray diffraction patterns. Thermal decomposition behavior of these complexes was also studied, and their kinetic thermodynamic parameters were calculated with Coats-Redfern and Horowitz-Metzger equations.

  2. Exploring Charge Transport in Guest Molecule Infiltrated Cu3(BTC)2 Metal Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Leonard, Francois Leonard [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Stavila, Vitalie [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Allendorf, Mark D. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2014-09-01

    The goal of this Exploratory Express project was to expand the understanding of the physical properties of our recently discovered class of materials consisting of metal-organic frameworks with electroactive ‘guest’ molecules that together form an electrically conducting charge-transfer complex (molecule@MOF). Thin films of Cu3(BTC)2 were grown on fused silica using solution step-by-step growth and were infiltrated with the molecule tetracyanoquinodimethane (TCNQ). The infiltrated MOF films were extensively characterized using optical microscopy, scanning electron microscopy, Raman spectroscopy, electrical conductivity, and thermoelectric properties. Thermopower measurements on TCNQ@Cu3(BTC)2 revealed a positive Seebeck coefficient of ~400 μV/k, indicating that holes are the primary carriers in this material. The high value of the Seebeck coefficient and the expected low thermal conductivity suggest that molecule@MOF materials may be attractive for thermoelectric power conversion applications requiring low cost, solution-processable, and non-toxic active materials.

  3. Spectrophotometric determination and thermodynamic studies of the charge transfer complexes of azelastine-HCl

    Directory of Open Access Journals (Sweden)

    Nahla N. Salama

    2011-06-01

    Full Text Available Three charge transfer complexes of azelastine as n-donor with π acceptors, dichloro-dicyanobenzoquinone (DDQ, chloranilic acid (CA and tetracyanoquinodimethane (TCNQ were prepared in acetonitrile. They yield a radical anions measured at 456, 520 and 841 nm within concentration ranges of 8.0–72, 40–320 and 1.6–14.4 μg mL−1 with good correlation coefficients (r = 0.9996–0.9998. The molar absorptivities and association constants for the colored products were evaluated using the Benesi–Hildebrand equation. The free energy change (ΔG0 and the enthalpy of formation (ΔH0 as well as the entropy (ΔS0 were determined for the reaction product with TCNQ. The methods were successfully applied to the analysis of azelastine in its pharmaceutical preparations, where no interferences could be observed from the additives commonly present in the eye drops or nasal spray as proved by good mean recoveries of 98.89 ± 1.06–99.54 ± 1.84%. The results were compared, favorably with the manufacturer method and validated according to ICH guidelines.

  4. Effects of solution viscosity on heterogeneous electron transfer across a liquid/liquid interface

    Energy Technology Data Exchange (ETDEWEB)

    Bai Yamin; Sun Peng; Zhang Meiqin; Gao Zhao; Yang Zhengyu; Shao Yuanhua

    2003-10-15

    Scanning electrochemical microscopy (SECM) is employed to investigate the effect of solution viscosity on the rate constants of electron transfer (ET) reaction between potassium ferricyanide in water and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in 1,2-dichloroethane. Either tetrabutylammonium (TBA{sup +}) or ClO{sub 4}{sup -} is chosen as the common ion in both phases to control the interfacial potential drop. The rate constant of heterogeneous ET reaction between TCNQ and ferrocyanide produced in-situ, k{sub 12}, is evaluated by SECM and is inversely proportional to the viscosity of the aqueous solution and directly proportional to the diffusion coefficient of K{sub 4}Fe(CN){sub 6} in water when the concentration of TCNQ in the DCE phase is in excess. The k{sub 12} dependence on viscosity is explained in terms of the longitudinal relaxation time of the solution. The rate constant of the heterogeneous ET reaction between TCNQ{sup -} and ferricyanide, k{sub 21}, is also obtained by SECM and these results cannot be explained by the same manner.

  5. Electrical properties of a charge-transfer interlayer modified organic heterojunction

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Shuwen; Salzmann, Ingo; Koch, Norbert [Humboldt-Universitaet zu Berlin (Germany). Institut f. Physik; Vollmer, Antje [HZB-BESSY, Berlin (Germany)

    2010-07-01

    We investigated the effect of a thin interlayer (ca. monolayer) of tetrafluoro-tetracyanoquinodimethane (F4-TCNQ) between prototypical hole and electron transport layers (HTL and ETL) on interface energetics and current transport. As HTL we used 4,4{sup '},4''-tris(N,N-diphenyl-amino)triphenylamine (TDATA) and tris (8-hydroxyquinoline)aluminium (Alq{sub 3}) as ETL, which are commonly employed in organic light emitting diodes. The hole injection barrier into TDATA is 0.5 eV, as measured by photoemission spectroscopy. Deposition of an F4-TCNQ interlayer on top of TDATA does not further change the energy level position. However, after applying the F4-TCNQ interlayer the energy levels of Alq3 deposited on top of TDATA are 0.15 eV closer to the Fermi-level than without the interlayer. Diodes fabricated without interlayer had a 0.6 V higher onset-voltage one order of magnitude lower current density than those with F4-TCNQ. These observations can be rationalized by an increased (non-radiative) electron-hole recombination rate at the modified organic heterojunction and a changed internal electric field distribution.

  6. Design of a macroalgae amperometric biosensor; application to the rapid monitoring of organophosphate insecticides in an agroecosystem.

    Science.gov (United States)

    Nunes, G S; Lins, J A P; Silva, F G S; Araujo, L C; Silva, F E P S; Mendonça, C D; Badea, M; Hayat, A; Marty, J-L

    2014-09-01

    The immobilization of enzymes onto transducer support is a mature technology and has been successfully implemented to improve biocatalytic processes for diverse applications. However, there exists still need to design more sophisticated and specialized strategies to enhance the functional properties of the biosensors. In this work, a biosensor platform based on innovative fabrication strategy was designed, and employed for the detection of organophosphate (OP) in natural waters. The biosensor was prepared by incorporating acetylcholinesterase enzyme (AChE) to the graphite paste modified with tetracyanoquinodimethane (TCNQ) mediator, along with the use of a macroalgae (Cladaphropsis membranous) as a functional immobilization support. The novel immobilization design resulted in a synergic effect, and led to enhanced stability and sensitivity of the biosensor. The designed biosensor was used to analyze methyl parathion OP insecticide in water samples collected from a demonstrably contaminated lake of São Luis Island, Maranhão, Northeast of Brazil. Water analysis revealed that the aquatic ecosystem was polluted by sub-ppm concentrations of the OP insecticide, and a good correlation was found between values obtained through biosensor and GC-MS techniques. Our results demonstrated that macroalgae-biosensor could be used as a low-cost and sensitive screening method to detect target analyte. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Quasi-steady-state voltammetry of rapid electron transfer reactions at the macroscopic substrate of the scanning electrochemical microscope.

    Science.gov (United States)

    Nioradze, Nikoloz; Kim, Jiyeon; Amemiya, Shigeru

    2011-02-01

    We report on a novel theory and experiment for scanning electrochemical microscopy (SECM) to enable quasi-steady-state voltammetry of rapid electron transfer (ET) reactions at macroscopic substrates. With this powerful approach, the substrate potential is cycled widely across the formal potential of a redox couple while the reactant or product of a substrate reaction is amperometrically detected at the tip in the feedback or substrate generation/tip collection mode, respectively. The plot of tip current versus substrate potential features the retraceable sigmoidal shape of a quasi-steady-state voltammogram although a transient voltammogram is obtained at the macroscopic substrate. Finite element simulations reveal that a short tip-substrate distance and a reversible substrate reaction (except under the tip) are required for quasi-steady-state voltammetry. Advantageously, a pair of quasi-steady-state voltammograms is obtained by employing both operation modes to reliably determine all transport, thermodynamic, and kinetic parameters as confirmed experimentally for rapid ET reactions of ferrocenemethanol and 7,7,8,8-tetracyanoquinodimethane at a Pt substrate with ∼0.5 μm-radius Pt tips positioned at 90 nm-1 μm distances. Standard ET rate constants of ∼7 cm/s were obtained for the latter mediator as the largest determined for a substrate reaction by SECM. Various potential applications of quasi-steady-state voltammetry are also proposed.

  8. Spectrofluorimetric determination of gemifloxacin mesylate and linezolid in pharmaceutical formulations: Application of quinone-based fluorophores and enhanced native fluorescence

    Directory of Open Access Journals (Sweden)

    Moussa Bahia Abbas

    2014-03-01

    Full Text Available Quinone-based fluorophores and enhanced native fluorescence techniques were applied for a fast quantitative analysis of gemifloxacin mesylate (GEM and linezolid (LIN in pharmaceutical formulations. For this purpose, three sensitive, accurate and precise spectrofluorimetric methods were developed. GEM, as an n-electron donor, reacts with 7,7,8,8-tetracyanoquinodimethane (method A and 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (method B as п-electron acceptors, forming charge transfer complexes that exhibit high fluorescence intensity at 441 and 390 nm upon excitation at 260 and 339 nm, respectively. Method C depends on measurement of enhanced native fluorescence of LIN in phosphate buffer (pH 5 at 380 nm upon excitation at 260 nm. Experimental factors affecting fluorescence intensity were optimized. Linearity was obtained over concentration ranges 50-500, 10-60 and 20-400 ng mL-1 for methods A, B and C, respectively. The developed methods were validated and successfully applied for determination of the cited drugs in tablets.

  9. X-ray diffraction, inelastic neutron scattering (INS) and infrared (IR) studies on 2:1 hexamethylbenzene (HMB)-tetracyanoethylene (TCNE) complex

    Energy Technology Data Exchange (ETDEWEB)

    Pawlukojc, A. [Joint Institute for Nuclear Research, 141980 Dubna (Russian Federation); Institute of Nuclear Chemistry and Technology, ul. Dorodna 16, 03-195 Warsaw (Poland); Sawka-Dobrowolska, W. [Faculty of Chemistry, University of Wroclaw, Joliot-Curie 14, 50-383 Wroclaw (Poland); Bator, G. [Faculty of Chemistry, University of Wroclaw, Joliot-Curie 14, 50-383 Wroclaw (Poland); Sobczyk, L. [Faculty of Chemistry, University of Wroclaw, Joliot-Curie 14, 50-383 Wroclaw (Poland)], E-mail: sobczyk@chem.uni.wroc.pl; Grech, E. [Institute of Chemistry and Environmental Protection, Szczecin University of Technology, Piastow Al. 12, 71-065 Szczecin (Poland); Nowicka-Scheibe, J. [Institute of Chemistry and Environmental Protection, Szczecin University of Technology, Piastow Al. 12, 71-065 Szczecin (Poland)

    2006-09-11

    The structure of the 2:1 hexamethylbenzene (HMB)-tetracyanoethylene (TCNE) complex was determined at 100 K. In the crystalline lattice the molecules of HMB (D) and TCNE (A) are arranged in DDADDADD stacks along the b-axis. Based on the red shift of the {nu}(C{identical_to}N) IR frequencies the charge transfer (CT) degree (Z) was estimated to be equal to 0.14. It is markedly higher than that for the complex of HMB with tetracyanoquinodimethane (TCNQ) for which Z = 0.06. The analysis of vibrational modes connected with torsional motion in the low frequency region was performed based on the inelastic neutron scattering (INS) experiments and DFT theoretical calculations. The correlation between {nu} {sub exp}/{nu} {sub calc} and {nu} {sub calc} shows a deviation of experimental values from calculated ones. It is the higher the lower is the frequency of the analysed mode. The comparison of correlations for neat HMB and its complexes with TCNQ and TCNE suggests that some role in decreasing the barrier to rotation can be played by the charge transfer between D and A molecules.

  10. X-ray diffraction, inelastic neutron scattering (INS) and infrared (IR) studies on 2:1 hexamethylbenzene (HMB)-tetracyanoethylene (TCNE) complex

    International Nuclear Information System (INIS)

    Pawlukojc, A.; Sawka-Dobrowolska, W.; Bator, G.; Sobczyk, L.; Grech, E.; Nowicka-Scheibe, J.

    2006-01-01

    The structure of the 2:1 hexamethylbenzene (HMB)-tetracyanoethylene (TCNE) complex was determined at 100 K. In the crystalline lattice the molecules of HMB (D) and TCNE (A) are arranged in DDADDADD stacks along the b-axis. Based on the red shift of the ν(C≡N) IR frequencies the charge transfer (CT) degree (Z) was estimated to be equal to 0.14. It is markedly higher than that for the complex of HMB with tetracyanoquinodimethane (TCNQ) for which Z = 0.06. The analysis of vibrational modes connected with torsional motion in the low frequency region was performed based on the inelastic neutron scattering (INS) experiments and DFT theoretical calculations. The correlation between ν exp /ν calc and ν calc shows a deviation of experimental values from calculated ones. It is the higher the lower is the frequency of the analysed mode. The comparison of correlations for neat HMB and its complexes with TCNQ and TCNE suggests that some role in decreasing the barrier to rotation can be played by the charge transfer between D and A molecules

  11. X-ray diffraction, inelastic neutron scattering (INS) and infrared (IR) studies on 2:1 hexamethylbenzene (HMB) tetracyanoethylene (TCNE) complex

    Science.gov (United States)

    Pawlukojć, A.; Sawka-Dobrowolska, W.; Bator, G.; Sobczyk, L.; Grech, E.; Nowicka-Scheibe, J.

    2006-09-01

    The structure of the 2:1 hexamethylbenzene (HMB)-tetracyanoethylene (TCNE) complex was determined at 100 K. In the crystalline lattice the molecules of HMB (D) and TCNE (A) are arranged in DDADDADD stacks along the b-axis. Based on the red shift of the ν(C tbnd N) IR frequencies the charge transfer (CT) degree ( Z) was estimated to be equal to 0.14. It is markedly higher than that for the complex of HMB with tetracyanoquinodimethane (TCNQ) for which Z = 0.06. The analysis of vibrational modes connected with torsional motion in the low frequency region was performed based on the inelastic neutron scattering (INS) experiments and DFT theoretical calculations. The correlation between νexp/ νcalc and νcalc shows a deviation of experimental values from calculated ones. It is the higher the lower is the frequency of the analysed mode. The comparison of correlations for neat HMB and its complexes with TCNQ and TCNE suggests that some role in decreasing the barrier to rotation can be played by the charge transfer between D and A molecules.

  12. Surface Charge Transfer Doping of Monolayer Phosphorene via Molecular Adsorption.

    Science.gov (United States)

    He, Yuanyuan; Xia, Feifei; Shao, Zhibin; Zhao, Jianwei; Jie, Jiansheng

    2015-12-03

    Monolayer phosphorene has attracted much attention owing to its extraordinary electronic, optical, and structural properties. Rationally tuning the electrical transport characteristics of monolayer phosphorene is essential to its applications in electronic and optoelectronic devices. Herein, we study the electronic transport behaviors of monolayer phosphorene with surface charge transfer doping of electrophilic molecules, including 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), NO2, and MoO3, using density functional theory combined with the nonequilibrium Green's function formalism. F4TCNQ shows optimal performance in enhancing the p-type conductance of monolayer phosphorene. Static electronic properties indicate that the enhancement is originated from the charge transfer between adsorbed molecule and phosphorene layer. Dynamic transport behaviors demonstrate that additional channels for hole transport in host monolayer phosphorene were generated upon the adsorption of molecule. Our work unveils the great potential of surface charge transfer doping in tuning the electronic properties of monolayer phosphorene and is of significance to its application in high-performance devices.

  13. Conductive Langmuir-Blodgett films. Doping with iodine or self-doping?

    International Nuclear Information System (INIS)

    Bourgoin, Jean-Philippe

    1991-01-01

    In this research thesis dealing with molecular architecture, the author reports the testing of two strategies aiming at reducing the importance of defects in conductive Langmuir-Blodgett films, and at enabling the production of conductive mono-molecular layer. According to the first strategy, conductive films are obtained after doping based on the use of iodine vapours of an insulating precursor film of molecules derived from BEDT-TTF. The so-produced films display a high conductivity and can be used as sensitive elements in gas sensors, but remain macroscopically insulating, probably because molecular reorganisation, as shown by a study based on different techniques (IR and UV linear dichroism, Raman spectroscopy, X ray diffraction), generates too many defects. The second strategy, self-doping, is based on a mixing of two derivatives of the same electro-active nucleus (the TCNQ, tetracyanoquinodimethane), an amphiphilic one and a semi-amphiphilic one. This strategy opens new perspectives in molecular engineering as it is a general way to produce conductive LB films from TCNQ [fr

  14. Doping graphene films via chemically mediated charge transfer

    Directory of Open Access Journals (Sweden)

    Ishikawa Ryousuke

    2011-01-01

    Full Text Available Abstract Transparent conductive films (TCFs are critical components of a myriad of technologies including flat panel displays, light-emitting diodes, and solar cells. Graphene-based TCFs have attracted a lot of attention because of their high electrical conductivity, transparency, and low cost. Carrier doping of graphene would potentially improve the properties of graphene-based TCFs for practical industrial applications. However, controlling the carrier type and concentration of dopants in graphene films is challenging, especially for the synthesis of p-type films. In this article, a new method for doping graphene using the conjugated organic molecule, tetracyanoquinodimethane (TCNQ, is described. Notably, TCNQ is well known as a powerful electron accepter and is expected to favor electron transfer from graphene into TCNQ molecules, thereby leading to p-type doping of graphene films. Small amounts of TCNQ drastically improved the resistivity without degradation of optical transparency. Our carrier doping method based on charge transfer has a huge potential for graphene-based TCFs.

  15. Highly sensitive multi-layer pressure sensor with an active nanostructured layer of an organic molecular metal

    International Nuclear Information System (INIS)

    Laukhin, V; Lebedev, V; Laukhina, E; Rovira, C; Veciana, J

    2016-01-01

    This work addresses to the modern technologies that need to be instrumented with lightweight highly sensitive pressure sensors. The paper presents the development of a new plain flexible thin pressure sensor using a nanostructured layer of the highly sensitive organic piezoresistive metal β-(BEDT-TTF) 2 I 3 as an active component; BEDT-TTF=bis (ethylenedithio)tetrathiafulvalene. The original construction approach permits one to operate the developed sensor on the principle of electrical resistance variations when its piezoresistive layer is elongated under a pressure increase. The pressure sensing element and a set of gold electrodes were integrated into one compact multi-layer design. The construction was optimized to enable one generic design for pressure ranges from 1 to 400 bar. The pressure tests showed that the sensor is able to control a small pressure change as a well definite electrical signal. So the developed type of the sensors is very attractive as a new generation of compact, lightweight, low-cost sensors that might monitor pressure with a good level of measurement accuracy. (paper)

  16. Recognition-Mediated Hydrogel Swelling Controlled by Interaction with a Negative Thermoresponsive LCST Polymer.

    Science.gov (United States)

    Belal, Khaled; Stoffelbach, François; Lyskawa, Joël; Fumagalli, Matthieu; Hourdet, Dominique; Marcellan, Alba; Smet, Lieselot De; de la Rosa, Victor R; Cooke, Graeme; Hoogenboom, Richard; Woisel, Patrice

    2016-11-02

    Most polymeric thermoresponsive hydrogels contract upon heating beyond the lower critical solution temperature (LCST) of the polymers used. Herein, we report a supramolecular hydrogel system that shows the opposite temperature dependence. When the non-thermosesponsive hydrogel NaphtGel, containing dialkoxynaphthalene guest molecules, becomes complexed with the tetra cationic macrocyclic host CBPQT 4+ , swelling occurred as a result of host-guest complex formation leading to charge repulsion between the host units, as well as an osmotic contribution of chloride counter-ions embedded in the network. The immersion of NaphtGel in a solution of poly(N-isopropylacrylamide) with tetrathiafulvalene (TTF) end groups complexed with CBPQT 4+ induced positive thermoresponsive behaviour. The LCST-induced dethreading of the polymer-based pseudorotaxane upon heating led to transfer of the CBPQT 4+ host and a concomitant swelling of NaphtGel. Subsequent cooling led to reformation of the TTF-based host-guest complexes in solution and contraction of the hydrogel. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  17. Synthesis, structure and physical properties of a new TTF derivative containing a PPD part

    International Nuclear Information System (INIS)

    Fujiwara, H; Sugishima, Y; Tsujimoto, K

    2008-01-01

    To develop new photo-conducting multi-functional materials, a new tetrathiafulvalene (TTF) derivative containing a 2,5-diphenyl-1,3,4-oxadiazole (PPD) moiety, in which the PPD part is connected directly to the TTF part with a single bond, was synthesized by the Pd(PPh 3 ) 4 -catalyzed Stille coupling reaction. X-Ray crystal structure analysis of the t-Butyl derivative (1) indicated the high planarity of the molecular skeleton and possible conduction pathways along the side-by-side direction of the TTF parts. Fluorescence from the PPD part of 1 was almost quenched by the intramolecular electron transfer from the electron-donating TTF part to the PPD part even when the PPD was irradiated by the excitation light of 315 nm. The single crystalline sample of the TCNQ complex of 1 (1-TCNQ) was prepared by a mixing method in CH 3 CN. The X-ray crystal structure analysis of 1-TCNQ revealed that there is PPD - TCNQ - TTF -type mixed stacking structure along the stacking direction, resulting in insulating behaviour of this complex.

  18. C sub 6 sub 0 fullerene and its molecular complexes under axial and shear deformation

    CERN Document Server

    Spitsina, N G; Bashkin, I V; Meletov, K P

    2002-01-01

    We have studied the pristine C sub 6 sub 0 and its molecular complexes with the organic donors bis(ethylenedithio) tetrathiafulvalene (BEDT-TTF or ET) and tetramethyltetraselenafulvalene (TMTSF) by means of ESR and Raman spectroscopy at high pressure. The important changes in the ESR signal of C sub 6 sub 0 were observed under axial pressure combined with shear deformation. It is shown that the treatment at a anisotropic pressure of 4 GPa results in a reduction in the symmetry of the C sub 6 sub 0 molecule and the formation of radicals. Treatment of the molecular complex of (ET) sub 2 centre dot C sub 6 sub 0 at a pressure of approx 4.5 GPa and a temperature of 150 deg. C leads to the formation of C sub 6 sub 0 dimers. The Raman spectra of the molecular complex C sub 6 sub 0 centre dot TMTSF centre dot 2(CS sub 2) were measured in situ at ambient temperature and pressures up to 9.5 GPa. The pressure behaviour of the Raman peaks reveals singularity at 5.0 +- 0.5 GPa related to the softening and splitting of so...

  19. Experimental and theoretical investigation of vibrational spectra of coordination polymers based on TCE-TTF.

    Science.gov (United States)

    Olejniczak, Iwona; Lapiński, Andrzej; Swietlik, Roman; Olivier, Jean; Golhen, Stéphane; Ouahab, Lahcène

    2011-08-01

    The room-temperature infrared and Raman spectra of a series of four isostructural polymeric salts of 2,3,6,7-tetrakis(2-cyanoethylthio)-tetrathiafulvalene (TCE-TTF) with paramagnetic (Co(II), Mn(II)) and diamagnetic (Zn(II), Cd(II)) ions, together with BF(4)(-) or ClO(4)(-) anions are reported. Infrared and Raman-active modes are identified and assigned based on theoretical calculations for neutral and ionized TCE-TTF using density functional theory (DFT) methods. It is confirmed that the TCE-TTF molecules in all the materials investigated are fully ionized and interact in the crystal structure through cyanoethylthio groups. The vibrational modes related to the C=C stretching vibrations of TCE-TTF are analyzed assuming the occurrence of electron-molecular vibration coupling (EMV). The presence of the antisymmetric C=C dimeric mode provides evidence that charge transfer takes place between TCE-TTF molecules belonging to neighboring polymeric networks. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. 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]dithiapent......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...

  1. The temperature dependence of the reflection intensities of the modulated composite structure Hg0.776(BEDT-TTF)SCN

    International Nuclear Information System (INIS)

    Pressprich, M.R.; Beek, C. van; Coppens, P.

    1994-01-01

    The temperature dependence between 30 and 300 K of the intensities of 24 reflections of the column-composite structure Hg 0.776 (BEDT-TTF)SCN [Wang, Beno, Carlson, Thorup, Murray, Porter, Williams, Maly, Bu, Petricek, Cisarova, Coppens, Jung, Whangbo, Shirber and Overmyer (1991). Chem. Mater. 3, 508-513; BEDT-TTF=3,4,3',4'-bis(ethylenedithio)-2,2',5,5'-tetrathiafulvalene] has been analyzed in terms of a model including phason temperature factors. The temperature dependence of the main and first-order satellite reflections is reasonably well reproduced in a refinement with 236 observations and four variables. The results are interpreted in terms of a temperature independence of the static displacement amplitudes. The room-temperature r.m.s. phason fluctuations of the mercury sublattice are 50(2) . This value implies that the mean mercury displacement amplitude will increase by ∝60% on lowering of the temperature to within the liquid-helium range. The thermal contraction on cooling is the same for the two sublattices. (orig.)

  2. A hybrid material based on [Mo6Br14]2- inorganic cluster units and [BEDO-TTF]+ organic monocationic radicals: Synthesis, structure and properties of (BEDO-TTF)2Mo6Br14(PhCN)4

    International Nuclear Information System (INIS)

    Kirakci, Kaplan; Hosoda, Hidemasa; Cordier, Stephane; Perrin, Christiane; Saito, Gunzi

    2006-01-01

    The first charge transfer salt based on non- dimerized [BEDO-TTF] + monocationic radical (BEDO-TTF=bis(ethylenedioxy)tetrathiafulvalene) associated with [Mo 6 Br 14 ] 2- cluster anions has been synthesized by conventional electro-oxidation and characterized by single crystal X-ray diffraction, UV-VIS-NIR absorption and magnetic susceptibility measurements. (BEDO-TTF) 2 Mo 6 Br 14 (PhCN) 4 crystallizes in the monoclinic system, space group P2 1 /n, a=10.414(4)A, b=21.711(7)A, c=15.958(5)A, β=93.65(3) o , V=3601(2)A 3 , Z=2, R 1 =0.0578, wR 2 =0.0731. The structure of this hybrid compound is built up from a [BEDO-TTF] + and PhCN (benzonitrile) organic framework in which are hosted the [Mo 6 Br 14 ] 2- inorganic cluster units. It results in non- dimerized [BEDO-TTF] + cations that exhibit a paramagnetic behavior characteristic of one unpaired electron

  3. Tetrathiapentalene-based organic conductors

    International Nuclear Information System (INIS)

    Misaki, Yohji

    2009-01-01

    The synthesis, structure and properties of tetrathiapentalene-based (TTP) organic conductors are reviewed. Among various TTP-type donors, bis-fused tetrathiafulvalene, 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (BDT-TTP) and its derivatives afford many metallic radical cation salts stable down to low temperatures, regardless of the size and shape of the counter anions. Most BDT-TTP conductors have a β-type donor arrangement with almost uniform stacks. Introduction of appropriate substituents results in molecular packing that differs from the β-type. A vinylogous TTP, 2-(1,3-dithiol-2-ylidene)-5-(2-ethanediylidene-1,3-dithiole) -1,3,4,6-tetrathiapentalene (DTEDT) has yielded an organic superconductor (DTEDT) 3 Au(CN) 2 as well as metallic radical cation salts, regardless of the counter anions. (Thio)pyran analogs of TTP, namely (T)PDT-TTP and its derivatives produce molecular conductors with novel molecular arrangements. A TTP analog with reduced π-electron system 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) has afforded several organic superconductors. Highly conducting molecular metals with unusual oxidation states (+1, +5/3 and neutral) have been developed on the basis of 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (BDT-TTP) derivatives and analogous metal derivatives M(dt) 2 (M = Ni, Au). (topical review)

  4. Photoinduced High-Frequency Charge Oscillations in Dimerized Systems

    Science.gov (United States)

    Yonemitsu, Kenji

    2018-04-01

    Photoinduced charge dynamics in dimerized systems is studied on the basis of the exact diagonalization method and the time-dependent Schrödinger equation for a one-dimensional spinless-fermion model at half filling and a two-dimensional model for κ-(bis[ethylenedithio]tetrathiafulvalene)2X [κ-(BEDT-TTF)2X] at three-quarter filling. After the application of a one-cycle pulse of a specifically polarized electric field, the charge densities at half of the sites of the system oscillate in the same phase and those at the other half oscillate in the opposite phase. For weak fields, the Fourier transform of the time profile of the charge density at any site after photoexcitation has peaks for finite-sized systems that correspond to those of the steady-state optical conductivity spectrum. For strong fields, these peaks are suppressed and a new peak appears on the high-energy side, that is, the charge densities mainly oscillate with a single frequency, although the oscillation is eventually damped. In the two-dimensional case without intersite repulsion and in the one-dimensional case, this frequency corresponds to charge-transfer processes by which all the bonds connecting the two classes of sites are exploited. Thus, this oscillation behaves as an electronic breathing mode. The relevance of the new peak to a recently found reflectivity peak in κ-(BEDT-TTF)2X after photoexcitation is discussed.

  5. Optical and Electrical Properties of TTF-MPcs (M = Cu, Zn Interfaces for Optoelectronic Applications

    Directory of Open Access Journals (Sweden)

    María Elena Sánchez-Vergara

    2015-11-01

    Full Text Available Sandwich structures were fabricated by a vacuum deposition method using MPc (M = Cu, Zn, with a Tetrathiafulvalene (TTF derivative, and Indium Tin Oxide (ITO and aluminum electrodes. The structure and morphology of the deposited films were studied by IR spectroscopy, scanning electron microscopy (SEM and energy dispersive spectroscopy (EDS. The absorption spectra of TTF derivative-MPc (M = Cu, Zn thin films deposited at room temperature were recorded in the spectral range 200–1000 nm. The optical band gap of the thin films was determined from the (αhν1/2 vs. hν plot. The direct-current (DC electrical properties of the glass/ITO/TTFderiv-MPc (M = Cu, Zn/Al structures were also investigated. Changes in conductivity of the derivative-TTF-enriched Pc compounds suggest the formation of alternative paths for carrier conduction. At low voltages, forward current density obeys an ohmic I-V relationship; at higher voltages, conduction is mostly due to a space-charge-limited conduction (SCLC mechanism.

  6. Integrated electrochemical gluconic acid biosensor based on self-assembled monolayer-modified gold electrodes. Application to the analysis of gluconic acid in musts and wines.

    Science.gov (United States)

    Campuzano, S; Gamella, M; Serra, B; Reviejo, A J; Pingarrón, J M

    2007-03-21

    An integrated amperometric gluconic acid biosensor constructed using a gold electrode (AuE) modified with a self-assembled monolayer (SAM) of 3-mercaptopropionic acid (MPA) on which gluconate dehydrogenase (GADH, 0.84 U) and the mediator tetrathiafulvalene (TTF, 1.5 micromol) were coimmobilized by covering the electrode surface with a dialysis membrane is reported. The working conditions selected were Eapp=+0.15 V and 25+/-1 degrees C. The useful lifetime of one single TTF-GADH-MPA-AuE was surprisingly long. After 53 days of continuous use, the biosensor exhibited 86% of the original sensitivity. A linear calibration plot was obtained for gluconic acid over the 6.0x10(-7) to 2.0x10(-5) M concentration range, with a limit of detection of 1.9x10(-7) M. The effect of potential interferents (glucose, fructose, galactose, arabinose, and tartaric, citric, malic, ascorbic, gallic, and caffeic acids) on the biosensor response was evaluated. The behavior of the biosensor in a flow-injection system in connection with amperometric detection was tested. The analytical usefulness of the biosensor was evaluated by determining gluconic acid in wine and must samples, and the results obtained were validated by comparison with those provided by using a commercial enzyme test kit.

  7. Charging a Li-O₂ battery using a redox mediator.

    Science.gov (United States)

    Chen, Yuhui; Freunberger, Stefan A; Peng, Zhangquan; Fontaine, Olivier; Bruce, Peter G

    2013-06-01

    The non-aqueous Li-air (O2) battery is receiving intense interest because its theoretical specific energy exceeds that of Li-ion batteries. Recharging the Li-O2 battery depends on oxidizing solid lithium peroxide (Li2O2), which is formed on discharge within the porous cathode. However, transporting charge between Li2O2 particles and the solid electrode surface is at best very difficult and leads to voltage polarization on charging, even at modest rates. This is a significant problem facing the non-aqueous Li-O2 battery. Here we show that incorporation of a redox mediator, tetrathiafulvalene (TTF), enables recharging at rates that are impossible for the cell in the absence of the mediator. On charging, TTF is oxidized to TTF(+) at the cathode surface; TTF(+) in turn oxidizes the solid Li2O2, which results in the regeneration of TTF. The mediator acts as an electron-hole transfer agent that permits efficient oxidation of solid Li2O2. The cell with the mediator demonstrated 100 charge/discharge cycles.

  8. Theoretical calculation of reorganization energy for electron self-exchange reaction by constrained density functional theory and constrained equilibrium thermodynamics.

    Science.gov (United States)

    Ren, Hai-Sheng; Ming, Mei-Jun; Ma, Jian-Yi; Li, Xiang-Yuan

    2013-08-22

    Within the framework of constrained density functional theory (CDFT), the diabatic or charge localized states of electron transfer (ET) have been constructed. Based on the diabatic states, inner reorganization energy λin has been directly calculated. For solvent reorganization energy λs, a novel and reasonable nonequilibrium solvation model is established by introducing a constrained equilibrium manipulation, and a new expression of λs has been formulated. It is found that λs is actually the cost of maintaining the residual polarization, which equilibrates with the extra electric field. On the basis of diabatic states constructed by CDFT, a numerical algorithm using the new formulations with the dielectric polarizable continuum model (D-PCM) has been implemented. As typical test cases, self-exchange ET reactions between tetracyanoethylene (TCNE) and tetrathiafulvalene (TTF) and their corresponding ionic radicals in acetonitrile are investigated. The calculated reorganization energies λ are 7293 cm(-1) for TCNE/TCNE(-) and 5939 cm(-1) for TTF/TTF(+) reactions, agreeing well with available experimental results of 7250 cm(-1) and 5810 cm(-1), respectively.

  9. Tuning the electronic structure and transport properties of graphene by noncovalent functionalization: effects of organic donor, acceptor and metal atoms

    International Nuclear Information System (INIS)

    Zhang Yonghui; Zhou Kaige; Xie Kefeng; Zeng Jing; Zhang Haoli; Peng Yong

    2010-01-01

    Using density functional theory and nonequilibrium Green's function (NEGF) formalism, we have theoretically investigated the binding of organic donor, acceptor and metal atoms on graphene sheets, and revealed the effects of the different noncovalent functionalizations on the electronic structure and transport properties of graphene. The adsorptions of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and tetrathiafulvalene (TTF) induce hybridization between the molecular levels and the graphene valence bands, and transform the zero-gap semiconducting graphene into a metallic graphene. However, the current versus voltage (I-V) simulation indicates that the noncovalent modifications by organic molecules are not sufficient to significantly alter the transport property of the graphene for sensing applications. We found that the molecule/graphene interaction could be dramatically enhanced by introducing metal atoms to construct molecule/metal/graphene sandwich structures. A chemical sensor based on iron modified graphene shows a sensitivity two orders of magnitude higher than that of pristine graphene. The results of this work could help to design novel graphene-based sensing or switching devices.

  10. 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.

  11. Doping Phosphorene with Holes and Electrons through Molecular Charge Transfer.

    Science.gov (United States)

    Vishnoi, Pratap; Rajesh, S; Manjunatha, S; Bandyopadhyay, Arkamita; Barua, Manaswee; Pati, Swapan K; Rao, C N R

    2017-11-03

    An important aspect of phosphorene, the novel two-dimensional semiconductor, is whether holes and electrons can both be doped in this material. Some reports found that only electrons can be preferentially doped into phosphorene. There are some theoretical calculations showing charge-transfer interaction with both tetrathiafulvalene (TTF) and tetracyanoethylene (TCNE). We have carried out an investigation of chemical doping of phosphorene by a variety of electron donor and acceptor molecules, employing both experiment and theory, Raman scattering being a crucial aspect of the study. We find that both electron acceptors and donors interact with phosphorene by charge-transfer, with the acceptors having more marked effects. All the three Raman bands of phosphorene soften and exhibit band broadening on interaction with both donor and acceptor molecules. First-principles calculations establish the occurrence of charge-transfer between phosphorene with donors as well as acceptors. The absence of electron-hole asymmetry is noteworthy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Rational design of organic superconductors through the use of the large, discrete molecular anions M(CF3)4-(M = Cu, Ag, Au) and SO3CF2CH2SF5-

    International Nuclear Information System (INIS)

    Schlueter, J.A.; Geiser, U.; Williams, J.M.

    1996-01-01

    A new approach to synthesis of organic superconductors has recently been pioneered which involves the use of large discrete molecular anions as the charge-compensating entities in these charge transfer salts. The organic electron-donor molecule bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) has been electrocrystallized with the novel organometallic M(CF 3 ) 4 - (M=Cu, Ag, Au) anions in a variety of 1,1,2-trihaloethane solvents. Over 20 organic superconductors have been synthesized which can be described by (ET) 2 M(CF 3 ) 4 (1,1,2- trihaloethane). These solvated salts are shown to have highly anisotropic physical properties which can be tuned via modifications of each of their three molecular components: ET electron donor molecule, M(CF 3 ) 4 - anion, and neutral 1,1,2- trihaloethane solvent molecule. Superconductivity has also been observed in an ET salt containing the discrete SF 5 CH 2 CF 2 SO 3 - anion with onset temperature near 5.2 K

  13. Microchip-calorimetry of organic charge transfer complex which shows superconductivity at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Muraoka, Yuki [Department of Chemistry, Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyonaka, Osaka 560-0043 (Japan); Yamashita, Satoshi [RIKEN, Hirosawa 2-1, Wako, Saitama 351-0198 (Japan); Yamamoto, Takashi [Department of Chemistry, Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyonaka, Osaka 560-0043 (Japan); Nakazawa, Yasuhiro, E-mail: nakazawa@chem.sci.osaka-u.ac.jp [Department of Chemistry, Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyonaka, Osaka 560-0043 (Japan); Institute for Molecular Science, Nishigonaka 38, Myodaiji, Okazaki 444-8585 (Japan)

    2012-03-20

    Highlights: Black-Right-Pointing-Pointer Organic charge transfer salt of {kappa}-(BEDT-TTF){sub 2}Cu[N(CN){sub 2}]Br shows superconductivity. Black-Right-Pointing-Pointer We succeeded to detect thermal anomaly microchip device TCG3880. Black-Right-Pointing-Pointer Development details of the calorimeter and the detection system is presented. Black-Right-Pointing-Pointer The magnetic fields dependence shows typical character of layered superconductor. - Abstract: We carried out thermodynamic measurements of organic charge transfer complex of {kappa}-(BEDT-TTF){sub 2}Cu[N(CN){sub 2}]Br, where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene by TCG3880 chip device in order to examine capability of the chip calorimeter at low temperature region and under magnetic fields. TCG3880 chip is mounted on a {sup 3}He cryostat available in combination with a superconductive magnet up to 7 T. Thermal anomalies related to the glass-like freezing of ethylene groups of BEDT-TTF molecules and the superconductive transition were observed. A frequency dependence of the thermal anomaly of the glass formation and a magnetic fields dependence of the thermal anomaly of the superconductive transition are reported. The results presented in this work demonstrate that the TCG3880 is quite useful for thermodynamic investigations of the organic charge transfer complex with much reduced sample quantity as compared with those of relaxation and adiabatic calorimetry.

  14. 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. Dithiaful......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......-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...... > OPE3-DTF > OPE3 irrespective of the tip metal. Rectification properties (or diode behavior) are observed in case of the Ag tip for which the work function is furthest from the HOMO levels of the OPE3s. Quantum chemical calculations of the transmission qualitatively agree with the experimental data...

  15. Attractive mechanical properties of a lightweight highly sensitive bi layer thermistor: polycarbonate/organic molecular conductor

    International Nuclear Information System (INIS)

    Laukhina, E; Lebedev, V; Rovira, C; Laukhin, V; Veciana, J

    2016-01-01

    The paper covers some of the basic mechanical characteristics of a recently developed bi layer thermistor: polycarbonate/(001) oriented layer of organic molecular conductor α’-(BEDT-TTF) 2 I x Br 3-x , were BEDT-TTF=bis(ethylenedithio)tetrathiafulvalen. The nano and macro mechanical properties have been studied in order to use this flexible, low cost thermistor in sensing applications by proper way. The nano-mechanical properties of the temperature sensitive semiconducting layer of α’-(BEDT-TTF) 2 I x Br 3-x were tested using nanoindentation method. The value of Young's modulus in direction being perpendicular to the layer plan was found as 9.0 ±1.4 GPa. The macro mechanical properties of the thermistor were studied using a 5848 MicroTester. The tensile tests showed that basic mechanical characteristics of the thermistor are close to those of polycarbonate films. This indicates a good mechanical strength of the developed sensor. Therefore, the thermistor can be used in technologies that need to be instrumented with highly robustness lightweight low cost temperature sensors. The paper also reports synthetic details on fabricating temperature sensing e-textile. As the temperature control is becoming more and more important in biomedical technologies like healthcare monitoring, this work strongly contributes on the ongoing research on engineering sensitive conducting materials for biomedical applications. (paper)

  16. Synthesis of block copolymers derived from N-trityl-(S)-serine and pyrene end-labeled poly(methyl methacrylate) or poly(N-isopropylacrylamide) via ATRP

    Energy Technology Data Exchange (ETDEWEB)

    Buruiana, Emil C., E-mail: emilbur@icmpp.ro [Petru Poni Institute of Macromolecular Chemistry, 41A Gr. Ghica Voda Alley 700487, Iasi (Romania); Podasca, Viorica; Buruiana, Tinca [Petru Poni Institute of Macromolecular Chemistry, 41A Gr. Ghica Voda Alley 700487, Iasi (Romania)

    2012-10-15

    A new monomer bearing N-trityl-L-serine methyl ester in structure, methacryloyloxyethyl carbamoyloxy-N-trityl methyl serine (MTS), was prepared to be further polymerized by atom transfer radical polymerization (ATRP) with pyrene-endcapped poly(methyl methacrylate) (Py-PMMA-Br) or poly(N-isopropylacrylamide) (Py-PNIPA-Br). The resulting block copolymers, poly(methyl methacrylate-block-methacryloyloxyethyl carbamoyloxy-N-trityl methyl serine) (Py-PMMA-b-PMTS) and poly(N-isopropylacrylamide-block-methacryloyloxyethyl carbamoyloxy-N-trityl methyl serine (Py-PNIPA-b-PMTS) were characterized by {sup 1}H ({sup 13}C) NMR, ultraviolet, FTIR and fluorescence spectroscopy, thermal analysis, differential scanning calorimetry (DSC), atomic force microscopy (AFM), scanning electron microscopy (SEM), and gel permeation chromatography (GPC) measurements. The chemical composition in Py-PMMA-b-PMTS was estimated from the {sup 1}H NMR analysis that indicated a ratio of the repeating units of 46:19 (MMA:MTS). For the Py-PNIPA-b-PMTS the composition rate in the copolymer was 61:25 (NIPA:MTS). Quenching of the pyrene species with N,N-diethylaniline, nitrobenzene, nitrophenol, potassium iodide, p-nitrotoluene and tetracyanoquinodimethane (TCNQ) in DMF solution excited at 348 nm was evidenced, more efficiently being nitrophenol and TCNQ. In this case, the monomer emission at 388-409 nm underwent a significant decrease caused of an electron transfer from the electron-reach photoexcited pyrene molecule to the electron-deficient quenchers. - Highlights: Black-Right-Pointing-Pointer Diblock copolymers combine the fluorescence of pyrene-PMMA (PNIPA) with the characteristics of PMTS. Black-Right-Pointing-Pointer Such copolymers could be used for nitroderivatives detecting. Black-Right-Pointing-Pointer UV/vis and fluorescence measurements give a good correlation for LCST of Py-PNIPA-Br.

  17. Enhanced Electrical Conductivity of Molecularly p-Doped Poly(3-hexylthiophene) through Understanding the Correlation with Solid-State Order

    KAUST Repository

    Hynynen, Jonna; Kiefer, David; Yu, Liyang; Kroon, Renee; Munir, Rahim; Amassian, Aram; Kemerink, Martijn; Mü ller, Christian

    2017-01-01

    Molecular p-doping of the conjugated polymer poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) is a widely studied model system. Underlying structure–property relationships are poorly understood because processing and doping are often carried out simultaneously. Here, we exploit doping from the vapor phase, which allows us to disentangle the influence of processing and doping. Through this approach, we are able to establish how the electrical conductivity varies with regard to a series of predefined structural parameters. We demonstrate that improving the degree of solid-state order, which we control through the choice of processing solvent and regioregularity, strongly increases the electrical conductivity. As a result, we achieve a value of up to 12.7 S cm–1 for P3HT:F4TCNQ. We determine the F4TCNQ anion concentration and find that the number of (bound + mobile) charge carriers of about 10–4 mol cm–3 is not influenced by the degree of solid-state order. Thus, the observed increase in electrical conductivity by almost 2 orders of magnitude can be attributed to an increase in charge-carrier mobility to more than 10–1 cm2 V–1 s–1. Surprisingly, in contrast to charge transport in undoped P3HT, we find that the molecular weight of the polymer does not strongly influence the electrical conductivity, which highlights the need for studies that elucidate structure–property relationships of strongly doped conjugated polymers.

  18. Enhanced Electrical Conductivity of Molecularly p-Doped Poly(3-hexylthiophene) through Understanding the Correlation with Solid-State Order

    KAUST Repository

    Hynynen, Jonna

    2017-10-11

    Molecular p-doping of the conjugated polymer poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) is a widely studied model system. Underlying structure–property relationships are poorly understood because processing and doping are often carried out simultaneously. Here, we exploit doping from the vapor phase, which allows us to disentangle the influence of processing and doping. Through this approach, we are able to establish how the electrical conductivity varies with regard to a series of predefined structural parameters. We demonstrate that improving the degree of solid-state order, which we control through the choice of processing solvent and regioregularity, strongly increases the electrical conductivity. As a result, we achieve a value of up to 12.7 S cm–1 for P3HT:F4TCNQ. We determine the F4TCNQ anion concentration and find that the number of (bound + mobile) charge carriers of about 10–4 mol cm–3 is not influenced by the degree of solid-state order. Thus, the observed increase in electrical conductivity by almost 2 orders of magnitude can be attributed to an increase in charge-carrier mobility to more than 10–1 cm2 V–1 s–1. Surprisingly, in contrast to charge transport in undoped P3HT, we find that the molecular weight of the polymer does not strongly influence the electrical conductivity, which highlights the need for studies that elucidate structure–property relationships of strongly doped conjugated polymers.

  19. Fabrication and characterization of p{sup +}-i-p{sup +} type organic thin film transistors with electrodes of highly doped polymer

    Energy Technology Data Exchange (ETDEWEB)

    Tadaki, Daisuke [Graduate School of Biomedical Engineering, Tohoku University, Sendai 980-8579 (Japan); Laboratory for Nanoelectronics and Spintronics, Research Institute of Electrical Communication, Tohoku University, Sendai 980-8577 (Japan); CREST, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012 (Japan); Ma, Teng; Niwano, Michio, E-mail: niwano@riec.tohoku.ac.jp [Laboratory for Nanoelectronics and Spintronics, Research Institute of Electrical Communication, Tohoku University, Sendai 980-8577 (Japan); CREST, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012 (Japan); Zhang, Jinyu; Iino, Shohei [Laboratory for Nanoelectronics and Spintronics, Research Institute of Electrical Communication, Tohoku University, Sendai 980-8577 (Japan); Hirano-Iwata, Ayumi [Graduate School of Biomedical Engineering, Tohoku University, Sendai 980-8579 (Japan); CREST, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012 (Japan); Kimura, Yasuo [CREST, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012 (Japan); Tokyo University of Technology, Hachioji, Tokyo 192-0982 (Japan); Rosenberg, Richard A. [Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439 (United States)

    2016-04-21

    Organic thin film transistors (OTFTs) have been explored because of their advantageous features such as light-weight, flexible, and large-area. For more practical application of organic electronic devices, it is very important to realize OTFTs that are composed only of organic materials. In this paper, we have fabricated p{sup +}-i-p{sup +} type of OTFTs in which an intrinsic (i) regioregular poly (3-hexylthiophene) (P3HT) layer is used as the active layer and highly doped p-type (p{sup +}) P3HT is used as the source and drain electrodes. The 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F{sub 4}-TCNQ) was used as the p-type dopant. A fabricating method of p{sup +}-i-p{sup +} OTFTs has been developed by using SiO{sub 2} and aluminum films as capping layers for micro-scaled patterning of the p{sup +}-P3HT electrodes. The characteristics of the OTFTs were examined using the photoelectron spectroscopy and electrical measurements. We demonstrated that the fabricated p{sup +}-i-p{sup +} OTFTs work with carrier injection through a built-in potential at p{sup +}/i interfaces. We found that the p{sup +}-i-p{sup +} OTFTs exhibit better FET characteristics than the conventional P3HT-OTFT with metal (Au) electrodes, indicating that the influence of a carrier injection barrier at the interface between the electrode and the active layer was suppressed by replacing the metal electrodes with p{sup +}-P3HT layers.

  20. Synthesis of block copolymers derived from N-trityl-(S)-serine and pyrene end-labeled poly(methyl methacrylate) or poly(N-isopropylacrylamide) via ATRP

    International Nuclear Information System (INIS)

    Buruiana, Emil C.; Podasca, Viorica; Buruiana, Tinca

    2012-01-01

    A new monomer bearing N-trityl-L-serine methyl ester in structure, methacryloyloxyethyl carbamoyloxy–N-trityl methyl serine (MTS), was prepared to be further polymerized by atom transfer radical polymerization (ATRP) with pyrene-endcapped poly(methyl methacrylate) (Py–PMMA–Br) or poly(N-isopropylacrylamide) (Py–PNIPA–Br). The resulting block copolymers, poly(methyl methacrylate–block–methacryloyloxyethyl carbamoyloxy–N-trityl methyl serine) (Py–PMMA–b–PMTS) and poly(N-isopropylacrylamide–block–methacryloyloxyethyl carbamoyloxy–N-trityl methyl serine (Py–PNIPA–b–PMTS) were characterized by 1 H ( 13 C) NMR, ultraviolet, FTIR and fluorescence spectroscopy, thermal analysis, differential scanning calorimetry (DSC), atomic force microscopy (AFM), scanning electron microscopy (SEM), and gel permeation chromatography (GPC) measurements. The chemical composition in Py–PMMA–b–PMTS was estimated from the 1 H NMR analysis that indicated a ratio of the repeating units of 46:19 (MMA:MTS). For the Py–PNIPA–b–PMTS the composition rate in the copolymer was 61:25 (NIPA:MTS). Quenching of the pyrene species with N,N-diethylaniline, nitrobenzene, nitrophenol, potassium iodide, p-nitrotoluene and tetracyanoquinodimethane (TCNQ) in DMF solution excited at 348 nm was evidenced, more efficiently being nitrophenol and TCNQ. In this case, the monomer emission at 388–409 nm underwent a significant decrease caused of an electron transfer from the electron-reach photoexcited pyrene molecule to the electron-deficient quenchers. - Highlights: ► Diblock copolymers combine the fluorescence of pyrene–PMMA (PNIPA) with the characteristics of PMTS. ► Such copolymers could be used for nitroderivatives detecting. ► UV/vis and fluorescence measurements give a good correlation for LCST of Py–PNIPA–Br.

  1. Enhanced electrocatalytic activity of MoSx on TCNQ-treated electrode for hydrogen evolution reaction

    KAUST Repository

    Chang, Yunghuang

    2014-10-22

    Molybdenum sulfide has recently attracted much attention because of its low cost and excellent catalytical effects in the application of hydrogen evolution reaction (HER). To improve the HER efficiency, many researchers have extensively explored various avenues such as material modification, forming hybrid structures or modifying geometric morphology. In this work, we reported a significant enhancement in the electrocatalytic activity of the MoSx via growing on Tetracyanoquinodimethane (TCNQ) treated carbon cloth, where the MoSx was synthesized by thermolysis from the ammonium tetrathiomolybdate ((NH4)2MoS4) precursor at 170 °C. The pyridinic N- and graphitic N-like species on the surface of carbon cloth arising from the TCNQ treatment facilitate the formation of Mo5+ and S2 2- species in the MoSx, especially with S2 2- serving as an active site for HER. In addition, the smaller particle size of the MoSx grown on TCNQ-treated carbon cloth reveals a high ratio of edge sites relative to basal plane sites, indicating the richer effective reaction sites and superior electrocatalytic characteristics. Hence, we reported a high hydrogen evolution rate for MoSx on TCNQ-treated carbon cloth of 6408 mL g-1 cm-2 h-1 (286 mmol g-1 cm-2 h-1) at an overpotential of V = 0.2 V. This study provides the fundamental concepts useful in the design and preparation of transition metal dichalcogenide catalysts, beneficial in the development in clean energy.

  2. Spectrophotometric determination and thermodynamic studies of the charge transfer complexation of emedastine difumarate with some π-acceptors

    Directory of Open Access Journals (Sweden)

    Abdel-Raeq A. Sawsan

    2017-05-01

    Full Text Available Spectrophotometric procedures were presented for the determination of antihistaminic drug, emedastine difumarate. The methods are based on the charge transfer complexation reaction of the drug with π-acceptors; 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, chloranilic acid (CA and 7,7,8,8-tetracyanoquinodimethane (TCNQ. Different charge-transfer complexes and colored radical anions were obtained. The formations of the colored complexes were utilized in the development of simple, rapid and accurate spectrophotometric methods for the analysis of emedastine in drug substance and products. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9996–0.9999 were found between the absorbance at the relevant maxima and the concentrations of emedastine in the range of 0.8–200 μg mL−1. The limits of detection ranged from 0.06 to 0.76 μg mL−1. The molar absorptivities and association constants for the colored complexes were evaluated using the Benesi–Hildebrand equation. The free energy change (ΔG° and the enthalpy of formation (ΔH° as well as the entropy (ΔS° were also determined. The methods were successfully applied to analyze the drug formulation with mean recovery percentages ± RSD% of 100.04 ± 0.59–100.22 ± 0.72. The results were compared favorably with the official and reported methods.

  3. Charge transfer complex of some nervous and brain drugs - Part 1: Synthesis, spectroscopic, analytical and biological studies on the reaction between haloperidol antipsychotic drugs with π-acceptors

    Science.gov (United States)

    El-Habeeb, Abeer A.; Al-Saif, Foziah A.; Refat, Moamen S.

    2013-02-01

    Donor-acceptor interactions between the electron donor haloperidol (HPL) and π-acceptors like 7,7,8,8-tetracyanoquinodimethane (TCNQ) and picric acid (PA) have been studied spectrophotometrically in CH3OH solvent. The donor-acceptor (charge transfer complexes) were discussed in terms of formation constant (KCT), molar extinction coefficient (ɛCT), standard free energy (ΔGo), oscillator strength (ƒ), transition dipole moment (μ), resonance energy (RN) and ionization potential (ID). The stoichiometry of these complexes was found to be 1:1 M ratio and having the formulas [(HPL)(TCNQ)] and [(HPL)(PA)], respectively. The charge transfer interaction was successfully applied to determine of HPL drug using mentioned common π-acceptors also, the results obtained herein are satisfactory for estimation of HPL compound in the pharmaceutical form. The formed solid charge-transfer complexes were also isolated and characterized using elemental analysis, conductivity, (infrared, Raman, and 1H NMR) spectra and X-ray powder diffraction (XRD). The experimental data of elemental analyses are in agreement with calculated data. The infrared spectra of both HPL complexes are confirming the participation of sbnd OH of 4-hydroxy-1-piperidyl moiety in the donor-acceptor chelation. The morphological surface of the resulted charge transfer complexes were investigated using scanning electron microscopy (SEM). The thermogravimetric analysis (TG/DTG) and differential scanning calorimetry (DSC) techniques were performed to give knowledge about the thermal stability behavior of the synthesized charge transfer complexes. Thermodynamic parameters were computed from the thermal decomposition data. These complexes were also tested for their antimicrobial activity against six different microorganisms, and the results were compared with the parent drug.

  4. Time-resolved terahertz spectroscopy of electrically conductive metal-organic frameworks doped with redox active species

    Science.gov (United States)

    Alberding, Brian G.; Heilweil, Edwin J.

    2015-09-01

    Metal-Organic Frameworks (MOFs) are three-dimensional coordination polymers that are well known for large pore surface area and their ability to adsorb molecules from both the gaseous and solution phases. In general, MOFs are electrically insulating, but promising opportunities for tuning the electronic structure exist because MOFs possess synthetic versatility; the metal and organic ligand subunits can be exchanged or dopant molecules can be introduced into the pore space. Two such MOFs with demonstrated electrical conductivity are Cu3(1,3,5-benzenetricarboxylate)2, a.k.a HKUST-1, and Cu[Ni(pyrazine-2,3-dithiolate)2]. Herein, these two MOFs have been infiltrated with the redox active species 7,7,8,8-tetracyanoquinodimethane (TCNQ) and iodine under solution phase conditions and shown to produce redox products within the MOF pore space. Vibrational bands assignable to TCNQ anion and triiodide anion have been observed in the Mid-IR and Terahertz ranges using FTIR Spectroscopy. The MOF samples have been further investigated by Time-Resolved Terehertz Spectroscopy (TRTS). Using this technique, the charge mobility, separation, and recombination dynamics have been followed on the picosecond time scale following photoexcitation with visible radiation. The preliminary results show that the MOF samples have small inherent photoconductivity with charge separation lifetimes on the order of a few picoseconds. In the case of HKUST-1, the MOF can also be supported by a TiO2 film and initial results show that charge injection into the TiO2 layer occurs with a comparable efficiency to the dye sensitizer N3, [cis-Bis(isothiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylato ruthenium(II)], and therefore this MOF has potential as a new light absorbing and charge conducting material in photovoltaic devices.

  5. The use of different glucose oxidases for the development of an amperometric reagentless glucose biosensor based on gold nanoparticles covered by polypyrrole

    International Nuclear Information System (INIS)

    German, Natalija; Kausaite-Minkstimiene, Asta; Ramanavicius, Arunas; Semashko, Tatiana; Mikhailova, Raisa; Ramanaviciene, Almira

    2015-01-01

    Graphical abstract: Display Omitted -- ABSTRACT: The amperometric glucose biosensors based on adsorbed electron transfer mediator (ETM) tetrathiafulvalene (TTF) or 1,10-phenanthroline-5,6-dione (PD) and glucose oxidase (GOx) from Aspergillus niger (GOx A.niger ), Penicillium adametzii (GOx P.adametzii ) or Penicillium funiculosum (GOx P.funiculosum ) cross-linked with glutaraldehyde were investigated. ETM and enzyme were immobilized layer by layer on bare graphite rod electrode (GR) premodified with gold nanoparticles (AuNP) of (i) 3.5 nm (GOx/ETM/AuNP 3.5 /GR), (ii) 6.0 nm (GOx/ETM/AuNP 6.0 /GR) and (iii) 13.0 nm (GOx/ETM/AuNP 13.0 /GR) size. The amperometric signals for all the developed biosensors were higher using PD in comparison with TTF. The biosensor based on GOx P.funiculosum showed higher analytical signal to glucose in a comparison to biosensors based on GOx A.niger and GOx P.adametzii . The registered current to glucose using GOx P.funiculosum /PD/AuNP 3.5 /GR electrode was linear in the glucose range from 0.1 to 10.0 mmol L −1 and the limit of detection was 0.024 mmol L −1 . Enzymatical synthesis of polypyrrole (Ppy) layer on the electrode was applied in order to expand the linear glucose detection range. After 22 h of polymerization the amperometric signal was linear in the glucose concentration range from 0.1 to 25.0 mmol L −1 , while after 69 h this rage was increased up to 50.0 mmol L −1 . Additionally Ppy layer on the electrode surface reduced the influence of interfering species on the amperometric signal. The performance of developed biosensor was investigated in human serum samples

  6. Speciation of chromium using chronoamperometric biosensors based on screen-printed electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Calvo-Pérez, Ana, E-mail: anacp@ubu.es; Domínguez-Renedo, Olga, E-mail: olgado@ubu.es; Alonso-Lomillo, MAsunción, E-mail: malomillo@ubu.es; Arcos-Martínez, MJulia, E-mail: jarcos@ubu.es

    2014-06-23

    Highlights: • Chronoamperometric determination of Cr(III) on tyrosinase based biosensors using SPCEs. • Chronoamperometric determination of Cr(VI) on GOx based biosensors using SPCEs. • High degree of sensitivity and selectivity in the analysis of both chromium species. • Bipotentiostatic chronoamperometric determination of both chromium species in the same sample. - Abstract: Chronoamperometric assays based on tyrosinase and glucose oxidase (GOx) inactivation have been developed for the monitoring of Cr(III) and Cr(VI). Tyrosinase was immobilized by crosslinking on screen-printed carbon electrodes (SPCEs) containing tetrathiafulvalene (TTF) as electron transfer mediator. The tyrosinase/SPC{sub TTF}E response to pyrocatechol is inhibited by Cr(III). This process, that is not affected by Cr(VI), allows the determination of Cr(III) with a capability of detection of 2.0 ± 0.2 μM and a reproducibility of 5.5%. GOx modified screen-printed carbon platinised electrodes (SPC{sub Pt}Es) were developed for the selective determination of Cr(VI) using ferricyanide as redox mediator. The biosensor was able to discriminate two different oxidation states of chromium being able to reject Cr(III) and to detect the toxic species Cr(VI). Chronoamperometric response of the biosensor towards glucose decreases with the presence of Cr(VI), with a capability of detection of 90.5 ± 7.6 nM and a reproducibility of 6.2%. A bipotentiostatic chronoamperometric biosensor was finally developed using a tyrosinase/SPC{sub TTF}E and a GOx/SPC{sub Pt}E connected in array mode for the simultaneous determination of Cr(III) and Cr(VI) in spiked tap water and in waste water from a tannery factory samples.

  7. Preparation of large-area molecular junctions with metallic conducting Langmuir–Blodgett films

    Energy Technology Data Exchange (ETDEWEB)

    Mochizuki, Kengo [Division of Marine Technology, Tokyo University of Marine Science and Technology, 2-1-6 Etchujima Koto-ku, Tokyo 135-8533 (Japan); Ohnuki, Hitoshi, E-mail: ohnuki@kaiyodai.ac.jp [Division of Marine Technology, Tokyo University of Marine Science and Technology, 2-1-6 Etchujima Koto-ku, Tokyo 135-8533 (Japan); Shimizu, Daisuke [Division of Marine Technology, Tokyo University of Marine Science and Technology, 2-1-6 Etchujima Koto-ku, Tokyo 135-8533 (Japan); Imakubo, Tatsuro [Department of Materials and Technology, Nagaoka University of Technology, 1603-1 Kamitomioka, Nagaoka, Niigata 940-2188 (Japan); Tsuya, Daiju [National Institute for Materials Science,1-2-1 Sengen, Tsukuba, Ibaraki 305-0047 (Japan); Izumi, Mitsuru [Division of Marine Technology, Tokyo University of Marine Science and Technology, 2-1-6 Etchujima Koto-ku, Tokyo 135-8533 (Japan)

    2014-03-03

    Metallic conducting Langmuir–Blodgett (LB) films were used as soft electrodes to fabricate molecular junctions with self-assembled monolayers (SAMs) of alkanethiols (CH{sub 3}(CH{sub 2}){sub n−1}SH) on an Au surface. Alkanethiols can form highly ordered, stable dielectric SAMs on metal surfaces over large areas. However, it is difficult to establish electrical contacts on such SAMs, which has limited their application. In this work, we used metallic conducting LB films composed of bis(ethylenedioxy)tetrathiafulvalene and stearic acid as a soft electrode onto alkanethiol SAMs (C{sub n}-SAM, n = 12, 14, 16, 18) to prepare Au/SAM/metal junctions of relatively large size (∼ 15.6 × 10{sup 3} μm{sup 2}). The current density–voltage (J–V) characteristics across the junctions exhibited rectifying behavior with a ratio R of ∼ 5 (R = |J(V)|/|J(− V)| at ± 1 V). The lower transfer rate corresponding to the electron transport from Au to the LB films exhibited nonlinear J–V characteristics, while the higher transfer rate of electrons from the LB film to Au showed linear J–V characteristics. Kelvin probe force microscopy revealed that the work function of the metallic LB films was smaller than that of Au. The observed rectification behavior is probably caused by different electron transport mechanisms between the two current directions. - Highlights: • Metallic Langmuir–Blodgett (LB) films were used as soft electrodes. • Molecular junctions of metal–alkanethiol–LB films were fabricated. • The current–voltage curve across the junctions exhibited rectifying behavior. • This is the first observation for alkanethiol monolayer junctions. • The work function difference between the electrodes induces the rectification.

  8. Tetrathiapentalene-based organic conductors

    Energy Technology Data Exchange (ETDEWEB)

    Misaki, Yohji, E-mail: misaki@eng.ehime-u.ac.j [Department of Applied Chemistry, Graduate School of Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577 (Japan)

    2009-04-15

    The synthesis, structure and properties of tetrathiapentalene-based (TTP) organic conductors are reviewed. Among various TTP-type donors, bis-fused tetrathiafulvalene, 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (BDT-TTP) and its derivatives afford many metallic radical cation salts stable down to low temperatures, regardless of the size and shape of the counter anions. Most BDT-TTP conductors have a {beta}-type donor arrangement with almost uniform stacks. Introduction of appropriate substituents results in molecular packing that differs from the {beta}-type. A vinylogous TTP, 2-(1,3-dithiol-2-ylidene)-5-(2-ethanediylidene-1,3-dithiole) -1,3,4,6-tetrathiapentalene (DTEDT) has yielded an organic superconductor (DTEDT){sub 3}Au(CN){sub 2} as well as metallic radical cation salts, regardless of the counter anions. (Thio)pyran analogs of TTP, namely (T)PDT-TTP and its derivatives produce molecular conductors with novel molecular arrangements. A TTP analog with reduced {pi}-electron system 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) has afforded several organic superconductors. Highly conducting molecular metals with unusual oxidation states (+1, +5/3 and neutral) have been developed on the basis of 2,5-bis(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene (BDT-TTP) derivatives and analogous metal derivatives M(dt){sub 2} (M = Ni, Au). (topical review)

  9. Speciation of chromium using chronoamperometric biosensors based on screen-printed electrodes

    International Nuclear Information System (INIS)

    Calvo-Pérez, Ana; Domínguez-Renedo, Olga; Alonso-Lomillo, MAsunción; Arcos-Martínez, MJulia

    2014-01-01

    Highlights: • Chronoamperometric determination of Cr(III) on tyrosinase based biosensors using SPCEs. • Chronoamperometric determination of Cr(VI) on GOx based biosensors using SPCEs. • High degree of sensitivity and selectivity in the analysis of both chromium species. • Bipotentiostatic chronoamperometric determination of both chromium species in the same sample. - Abstract: Chronoamperometric assays based on tyrosinase and glucose oxidase (GOx) inactivation have been developed for the monitoring of Cr(III) and Cr(VI). Tyrosinase was immobilized by crosslinking on screen-printed carbon electrodes (SPCEs) containing tetrathiafulvalene (TTF) as electron transfer mediator. The tyrosinase/SPC TTF E response to pyrocatechol is inhibited by Cr(III). This process, that is not affected by Cr(VI), allows the determination of Cr(III) with a capability of detection of 2.0 ± 0.2 μM and a reproducibility of 5.5%. GOx modified screen-printed carbon platinised electrodes (SPC Pt Es) were developed for the selective determination of Cr(VI) using ferricyanide as redox mediator. The biosensor was able to discriminate two different oxidation states of chromium being able to reject Cr(III) and to detect the toxic species Cr(VI). Chronoamperometric response of the biosensor towards glucose decreases with the presence of Cr(VI), with a capability of detection of 90.5 ± 7.6 nM and a reproducibility of 6.2%. A bipotentiostatic chronoamperometric biosensor was finally developed using a tyrosinase/SPC TTF E and a GOx/SPC Pt E connected in array mode for the simultaneous determination of Cr(III) and Cr(VI) in spiked tap water and in waste water from a tannery factory samples

  10. Gold and Nickel Extended Thiophenic-TTF Bisdithiolene Complexes

    Directory of Open Access Journals (Sweden)

    Rafaela A. L. Silva

    2018-02-01

    Full Text Available Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu4N[Au(α-mtdt2] (3 and nickel dianionic species (n-Bu4Nx[Ni(α-mtdt2] (x = 1,2 (4 were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene bisdithiolenes. However the introduction of the large, bulky substituent tert-butyl, led to the formation of a Au (I dinuclear complex, (n-Bu4N2[Au2(α-tbtdt2] (5. The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt2] (6 and [Ni(α-mtdt2] (7 polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt2] (6 presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt2] (7 large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt2] are indicative that these compounds are single component molecular conductors.

  11. The nature of the [TTF]˙+···[TTF]˙+ interactions in the [TTF]2(2+) dimers embedded in charged [3]catenanes: room-temperature multicenter long bonds.

    Science.gov (United States)

    Capdevila-Cortada, Marçal; Novoa, Juan J

    2012-04-23

    The properties of tetrathiafulvalene dimers ([TTF](2)(2+)) and the functionalized ring-shaped bispropargyl (BPP)-functionalized TTF dimers, [BPP-TTF](2)(2+), found at room temperature in charged [3]catenanes, were evaluated by M06L calculations. The results showed that their isolated [TTF](2)(2+) and [BPP-TTF](2)(2+) dimers are energetically unstable towards dissociation. When enclosed in the 4(+)-charged central cyclophane ring of charged [3]catenanes (CBPQT(4+)), [TTF](2)(2+) and [BPP-TTF](2)(2+) dimers are also energetically unstable with respect to leaving the CBPQT(4+) ring; since the barrier for the exiting process is only about 3 kcal mol(-1), that is, within the reach of thermal energies at room temperature (neutral [TTF](2)(0) dimers are stable within the CBPQT(4+) ring). However, the [BPP-TTF](2)(2+) dimers in charged [3]catenanes cannot exit, because this would imply breaking the covalent bonds of the BPP-TTF(+) macrocycle. Finally, it was shown that the [TTF](2)(2+), [BPP-TTF](2)(2+) dimers, and charged [3]catenanes are energetically stable in solution and in crystals of their salts, in the first case due to the interactions with the solvent, and in the second case mostly due to cation-anion interactions. In these environmental conditions at room temperature the TTF units of the [BPP-TTF](2)(2+) dimers make short contacts, thus allowing their SOMO orbitals to overlap: a room-temperature multicenter long bond is formed, similar to those previously found in other [TTF](2)(2+) salts and their solutions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Integrated multienzyme electrochemical biosensors for the determination of glycerol in wines.

    Science.gov (United States)

    Gamella, M; Campuzano, S; Reviejo, A J; Pingarrón, J M

    2008-02-25

    The construction and performance of integrated amperometric biosensors for the determination of glycerol are reported. Two different biosensor configurations have been evaluated: one based on the glycerol dehydrogenase/diaphorase (GDH/DP) bienzyme system, and another using glycerol kinase/glycerol-3-phosphate oxidase/peroxidase (GK/GPOx/HRP). Both enzyme systems were immobilized together with the 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 +150mV (vs. Ag/AgCl), and the reduction of TTF(+) at 0mV were used for the monitoring of the enzyme reactions for the bienzyme and trienzyme configurations, respectively. Experimental variables concerning both the biosensors composition and the working conditions were optimized for each configuration. A good repeatability of the measurements with no need of cleaning or pretreatment of the biosensors was obtained in both cases. After 51 days of use, the GDH/DP biosensor still exhibited 87% of the original sensitivity, while the GK/GPOx/HRP biosensor yielded a 46% of the original response after 8 days. Calibration graphs for glycerol with linear ranges of 1.0x10(-6) to 2.0x10(-5) or 1.0x10(-6) to 1.0x10(-5)M glycerol and sensitivities of 1214+/-21 or 1460+/-34microAM(-1) were obtained with GDH/DP and GK/GPOx/HRP biosensors, respectively. The calculated detection limits were 4.0x10(-7) and 3.1x10(-7)M, respectively. The biosensors exhibited a great sensitivity with no significant interferences in the analysis of wines. The biosensors were applied to the determination of glycerol in 12 different wines and the results advantageously compared with those provided by a commercial enzyme kit.

  13. Optical absorption and electrical properties of MPc (M =Fe, Cu, Zn)-TCNQ interfaces for optoelectronic applications

    Science.gov (United States)

    Sánchez Vergara, M. E.; Medrano Gallardo, D.; Vera Estrada, I. L.; Jiménez Sandoval, O.

    2018-04-01

    This research is related to the growth and characterization of doped molecular semiconductor metallophthalocyanine-tetracyanoquinodimethane (MPc-TCNQ) films, with M = Fe, Zn, Cu. FT-IR and Raman spectroscopies were employed to study the chemical interactions taking place in the MPc-TCNQ films. XRD was carried out to determine the crystalline structure present in the samples, due to the facility of the MPcs to be in alpha and/or beta phases. The thin films were analized by SEM and UV-vis spectroscopy in order to study their morphological and optical properties. The absorption spectra recorded in the UV-Vis region for the deposited samples showed two bands, namely the Q and Soret bands. The absorption coefficient (α) and photon energy (hν) were calculated from the UV-vis spectra, to in turn determine the optic activation energy in each film and its semiconductor behavior. The values obtained for direct transitions due to the crystallinity of the films were: 1.2, 1.4 and 2 eV for FePc-TCNQ (MMFe), ZnPc-TCNQ (MMZn) and CuPc-TCNQ (MMCu), respectively. Additionally, I-V characteristics have been obtained from fabricated glass/ITO/MM/Ag devices using ohmic contacts both after annealing. The electrical properties of the devices, e.g. carrier mobility and concentration of thermally generated holes, were extracted from the J-V characteristics. The results show that the conduction process is ohmic for the MMZn and MMCu devices, at low voltages, while at high voltages, a space-charge-limited conduction (SCLC) is present. The effect of temperature on conductivity was also measured in these samples and the lower thermal activation energy calculated was 0.37 eV for MMZn. Moreover, it was found that the temperature-dependent electric current is always higher for the MMZn device and suggests a semiconductor-like behavior with an important conductivity of the order of 103 S cm-1. Anyhow, in terms not only of electric properties, but also of optic behavior, the results suggest that

  14. Localized, stepwise template growth of functional nanowires from an amino acid-supported framework in a microfluidic chip.

    Science.gov (United States)

    Puigmartí-Luis, Josep; Rubio-Martínez, Marta; Imaz, Inhar; Cvetković, Benjamin Z; Abad, Llibertat; Pérez Del Pino, Angel; Maspoch, Daniel; Amabilino, David B

    2014-01-28

    A spatially controlled synthesis of nanowire bundles of the functional crystalline coordination polymer (CP) Ag(I)TCNQ (tetracyanoquinodimethane) from previously fabricated and trapped monovalent silver CP (Ag(I)Cys (cysteine)) using a room-temperature microfluidic-assisted templated growth method is demonstrated. The incorporation of microengineered pneumatic clamps in a two-layer polydimethylsiloxane-based (PDMS) microfluidic platform was used. Apart from guiding the formation of the Ag(I)Cys coordination polymer, this microfluidic approach enables a local trapping of the in situ synthesized structures with a simple pneumatic clamp actuation. This method not only enables continuous and multiple chemical events to be conducted upon the trapped structures, but the excellent fluid handling ensures a precise chemical activation of the amino acid-supported framework in a position controlled by interface and clamp location that leads to a site-specific growth of Ag(I)TCNQ nanowire bundles. The synthesis is conducted stepwise starting with Ag(I)Cys CPs, going through silver metal, and back to a functional CP (Ag(I)TCNQ); that is, a novel microfluidic controlled ligand exchange (CP → NP → CP) is presented. Additionally, the pneumatic clamps can be employed further to integrate the conductive Ag(I)TCNQ nanowire bundles onto electrode arrays located on a surface, hence facilitating the construction of the final functional interfaced systems from solution specifically with no need for postassembly manipulation. This localized self-supported growth of functional matter from an amino acid-based CP shows how sequential localized chemistry in a fluid cell can be used to integrate molecular systems onto device platforms using a chip incorporating microengineered pneumatic tools. The control of clamp pressure and in parallel the variation of relative flow rates of source solutions permit deposition of materials at different locations on a chip that could be useful for device

  15. On the importance of developing a new generation of breath tests for Helicobacter pylori detection.

    Science.gov (United States)

    Kushch, Ievgeniia; Korenev, Nikolai; Kamarchuk, Lyudmila; Pospelov, Alexander; Kravchenko, Andrey; Bajenov, Leonid; Kabulov, Mels; Amann, Anton; Kamarchuk, Gennadii

    2015-12-15

    State-of-the-art methods for non-invasive detection of the Helicobacter pylori (H. pylori) infection have been considered. A reported global tendency towards a non-decreasing prevalence of H. pylori worldwide could be co-influenced by the functional limitations of urea breath tests (UBTs), currently preferred for the non-invasive recognition of H. pylori in a clinical setting. Namely, the UBTs can demonstrate false-positive or false-negative results. Within this context, limitations of conventional clinically exploited H. pylori tests have been discussed to justify the existing need for the development of a new generation of breath tests for the detection of H. pylori and the differentiation of pathogenic and non-pathogenic strains of the bacterium. This paper presents the results of a pilot clinical study aimed at evaluating the development and diagnostic potential of a new method based on the detection of the non-urease products of H. pylori vital activity in exhaled gas. The characteristics of breath of adolescents with H. pylori-positive and H. pylori-negative functional dyspepsia, together with a consideration of the cytotoxin-associated gene A (CagA) status of H. pylori-positive subjects, have been determined for the first time using innovative point-contact nanosensor devices based on salts of the organic conductor tetracyanoquinodimethane (TCNQ). The clinical and diagnostic relevance of the response curves of the point-contact sensors was assessed. It was found that the recovery time of the point-contact sensors has a diagnostic value for differentiation of the H. pylori-associated peptic ulcer disease. The diagnostically significant elongation of the recovery time was even more pronounced in patients infected with CagA-positive H. pylori strains compared to the CagA-negative patients. Taking into account the operation of the point-contact sensors in the real-time mode, the obtained results are essential prerequisites for the development of a fast and

  16. Zero-Field Spin Structure and Spin Reorientations in Layered Organic Antiferromagnet, κ-(BEDT-TTF)2Cu[N(CN)2]Cl, with Dzyaloshinskii-Moriya Interaction

    Science.gov (United States)

    Ishikawa, Rui; Tsunakawa, Hitoshi; Oinuma, Kohsuke; Michimura, Shinji; Taniguchi, Hiromi; Satoh, Kazuhiko; Ishii, Yasuyuki; Okamoto, Hiroyuki

    2018-06-01

    Detailed magnetization measurements enabled us to claim that the layered organic insulator κ-(BEDT-TTF)2Cu[N(CN)2]Cl [BEDT-TTF: bis(ethylenedithio)tetrathiafulvalene] with the Dzyaloshinskii-Moriya interaction has an antiferromagnetic spin structure with the easy axis being the crystallographic c-axis and the net canting moment parallel to the a-axis at zero magnetic field. This zero-field spin structure is significantly different from that proposed in the past studies. The assignment was achieved by arguments including a correction of the direction of the weak ferromagnetism, reinterpretations of magnetization behaviors, and reasoning based on known high-field spin structures. We suggest that only the contributions of the strong intralayer antiferromagnetic interaction, the moderately weak Dzyaloshinskii-Moriya interaction, and the very weak interlayer ferromagnetic interaction can realize this spin structure. On the basis of this model, characteristic magnetic-field dependences of the magnetization can be interpreted as consequences of intriguing spin reorientations. The first reorientation is an unusual spin-flop transition under a magnetic field parallel to the b-axis. Although the existence of this transition is already known, the interpretation of what happens at this transition has been significantly revised. We suggest that this transition can be regarded as a spin-flop phenomenon of the local canting moment. We also claim that half of the spins rotate by 180° at this transition, in contrast to the conventional spin flop transition. The second reorientation is the gradual rotation of the spins during the variation of the magnetic field parallel to the c-axis. In this process, all the spins rotate around the Dzyaloshinskii-Moriya vectors by 90°. The results of our simulation based on the classical spin model well reproduce these spin reorientation behaviors, which strongly support our claimed zero-field spin structure. The present study highlights the

  17. I: Hydrodynamic-focusing microreactor II: Mechanically interlocked molecules for functional materials

    Science.gov (United States)

    Coti, Karla Karina

    , tetrathiafulvalene and 1,5-dioxynapthalene as the recognition units -- can be exploited to develop new electro-optical liquid crystalline (LC) materials, a novel cholesteric LC bistable [2]rotaxane has been designed (Chapter 3) and its synthesis is underway. Furthermore, the electrochromic behavior of Smectic A LC bistable Rlrotaxanes has been accomplished (Chapter 4) in the condensed LC state as well as within a PMMA polymer matrix.

  18. Structural and electronic properties of epitaxial graphene on SiC(0 0 0 1): a review of growth, characterization, transfer doping and hydrogen intercalation

    International Nuclear Information System (INIS)

    Riedl, C; Coletti, C; Starke, U

    2010-01-01

    Graphene, a monoatomic layer of graphite, hosts a two-dimensional electron gas system with large electron mobilities which makes it a prospective candidate for future carbon nanodevices. Grown epitaxially on silicon carbide (SiC) wafers, large area graphene samples appear feasible and integration in existing device technology can be envisioned. This paper reviews the controlled growth of epitaxial graphene layers on SiC(0 0 0 1) and the manipulation of their electronic structure. We show that epitaxial graphene on SiC grows on top of a carbon interface layer that-although it has a graphite-like atomic structure-does not display the linear π-bands typical for graphene due to a strong covalent bonding to the substrate. Only the second carbon layer on top of this interface acts like monolayer graphene. With a further carbon layer, a graphene bilayer system develops. During the growth of epitaxial graphene on SiC(0 0 0 1) the number of graphene layers can be precisely controlled by monitoring the π-band structure. Experimental fingerprints for in situ growth control could be established. However, due to the influence of the interface layer, epitaxial graphene on SiC(0 0 0 1) is intrinsically n-doped and the layers have a long-range corrugation in their density of states. As a result, the Dirac point energy where the π-bands cross is shifted away from the Fermi energy, so that the ambipolar properties of graphene cannot be exploited. We demonstrate methods to compensate and eliminate this structural and electronic influence of the interface. We show that the band structure of epitaxial graphene on SiC(0 0 0 1) can be precisely tailored by functionalizing the graphene surface with tetrafluoro-tetracyanoquinodimethane (F4-TCNQ) molecules. Charge neutrality can be achieved for mono- and bilayer graphene. On epitaxial bilayer graphene, where a band gap opens due to the asymmetric electric field across the layers imposed by the interface, the magnitude of this band gap

  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. Enhancing the open-circuit voltage of dye-sensitized solar cells: coadsorbents and alternative redox couples[Dissertation 4066

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Z.

    2008-04-15

    this effect. The voltage shift was interpreted as the effect of a negative shift in conduction band and a decrease in the back electron transfer of photoinjected electrons in TiO{sub 2} to the triiodide species in the electrolyte, the former being the main reason for the large photovoltage increase. The specificity in the structure of the coadsorbents and its implication were also discussed. In Chapters 8 and 9, we studied the possibility to use some one-electron transfer couples as the replacement of the iodide-based electrolyte. Mainly, 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO), phenoxazine derivatives and tetrathiafulvalene were selected as the candidates and their device performances were evaluated by electrochemical, photochemical and phototransient measurements. The redox potentials of these couples were 100 to 400 mV more positive than that of I{sup -} / I{sub 3}{sup -} couple, mitigating the potential mismatch between the Nernst potential of the dye cation and that of the redox mediator. TEMPO/TEMPO{sup +} based devices showed the best conversion efficiency of more than 5 % under AM 1.5 illumination at 100 mWcm{sup -2}, a new record at this light intensity for non-iodine and non-pseudohologen electrolytes. On the other hand, the fast recapture of electrons in TiO{sub 2} by the oxidized species of the couple was accounted for the lower observed increase in V{sub oc} of the devices with these electrolytes than the simple shift in the redox potentials. We drew some final conclusions in Chapter 10 together with our outlooks in the future research and development of coadsorbents and electrolytes for dye-sensitized solar cells. (author)

  1. 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

  2. From surfaces to magnetic properties: special section dedicated to Juan Rojo

    Science.gov (United States)

    Mascaraque, A.; Rodríguez de la Fuente, O.; González-Barrio, Miguel A.

    2013-12-01

    by Barandiarán et al. In the following paper, Crespo et al review the effect of organic and inorganic coatings on magnetic nanoparticles, showing that the coating can tune the magnetic properties of metallic and oxide nano-sized particles. Barja et al report on ordered magnetic ion structures formed by evaporation of Mn and Fe on self-assembled layers of tetracyanoquinodimethane (TCNQ) molecules on Cu(111). Finally, Rodríguez de la Fuente et al investigate the role of surface defects on the physico-chemical properties of metals and oxides in a variety of scenarios, showing how the surface controls the mechanical properties probed at the nanoscale or the chemical reactivity. Acknowledgments The editors are grateful to all the invited contributors to this special section of Journal of Physics: Condensed Matter . We also thank the staff of IOP Publishing for handling the administrative matters and the refereeing process, and for their patience and helpful disposition. From surfaces to magnetic properties contents From surfaces to magnetic properties: special section dedicated to Juan RojoA Mascaraque, O Rodríguez de la Fuente and Miguel A González-Barrio Juan Rojo: the surface science and science politics maker in SpainA Mascaraque, O Rodríguez de la Fuente, Miguel A González-Barrio, Javier Solana, Luis Oro and Ana Crespo Initial stages of FeO growth on Ru(0001)I Palacio, M Monti, J F Marco, K F McCarty and J de la Figuera Surprising resistivity decrease in manganites with constant electronic densityR Cortés-Gil, M L Ruiz-González, J M Alonso, J L Martínez, A Hernando, M Vallet-Regí, and J M González-Calbet Thermoseeds for interstitial magnetic hyperthermia: from bioceramics to nanoparticlesA Baeza, D Arcos and M Vallet-Regí Revisited magnetic phase diagram for CeNi1-xCux system: spin-glass in the weak interaction limitN Marcano, J I Espeso and J C Gómez Sal Magnetic field and atomic order effect on the martensitic transformation of a metamagnetic alloyJ M

  3. Design and Synthesis of Nonequilibrium Systems.

    Science.gov (United States)

    Cheng, Chuyang; McGonigal, Paul R; Stoddart, J Fraser; Astumian, R Dean

    2015-09-22

    The active transport of ions and molecules across cell membranes is essential to creating the concentration gradients that sustain life in all living organisms, be they bacteria, fungi, plants, animals or Homo sapiens. Nature uses active transport everywhere for everything. Molecular biologists have long been attracted to the study of active transport and continue to this day to investigate and elucidate the tertiary structures of the complex motor proteins that sustain it, while physicists, interested in nonequilibrium statistical mechanics, have developed theoretical models to describe the driven ratcheting motions that are crucial to its function. The increasingly detailed understanding that contemporary science has acquired relating to active transport, however, has yet to lead to the design and construction of artificial molecular motors capable of employing ratchet-driven motions that can also perform work against concentration gradients. Mechanically interlocked molecules (MIMs) in the form of pseudo- and semirotaxanes are showing some encouraging signs in meeting these goals. This review summarizes recent progress in making artificial molecular motors that can perform work by "pumping" tetracationic rings into high-energy states. The launching pad is a bistable [2]rotaxane whose dumbbell component contains two electron-donating recognition sites, one, a tetrathiafulvalene (TTF) unit, which interacts more strongly with the ring component, cyclobis(paraquat-p-phenylene) (CBPQT(4+)), containing two electron-accepting bipyridinium units, than does the other 1,5-dioxynaphthalene (DNP) unit. Switching can be induced electrochemically by oxidizing the TTF unit to a TTF(•+) radical cation, whereupon Coulombic repulsion takes care of moving the ring to the DNP unit. Reduction of the radical cation resets the switch. Molecular switches operate at, or close to, equilibrium. Any work done during one switching event is undone during the reset. Molecular motors, on the