- Synthesis of Unsymmetrical Tetrathiafulvalenes and Electrical Conductivities of Their Tetracyanoquinodimethane Complexes
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The preparation of some unsymmetrical tetrathiafulvalenes and the electrical conductivities of their charge transfer complexes with tetracyanoquinodimethane (TCNQ) are described; the ethylenedithio(trimethylene)tetrathiafulvalene-TCNQ complex exhibited higher conductivity than complexes of tetrathiafulvalene, tetramethyltetrathiafulvalene, and hexamethylenetetrathiafulvalene with TCNQ.
- Tatemitsu, Hitoshi,Nishikawa, Etsushi,Sakata, Yoshiteru,Misumi, Soichi
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- Preparation of Methyl Chalcogenated Derivatives of 1,4,5,8-Tetrathiatetralin
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Tetrakis(methylthio)-1,4,5,8-tetrathiatetralin 4 and tetrakis(methylseleno)-1,4,5,8-tetrathiatetralin 6 is successfully prepared by the reaction of tetrathiatetralin (TTT) 2 with lithium diissopropylamide and MeSSMe or MeSeSeMe in diethyl ether and a remarkable solvent effect is observed in the analogous reaction in tetrahydrofuran to give tetrakis(methylthio)tetrathiafulvalene 5 by a novel rearrangement.
- Nakatsuji, Shin'ichi,Amano, Yoshiki,Kawamura, Haruki,Anzai, Hiroyuki
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- SULFUR-CONTAINING CARBENE-METAL COMPOUNDS: GENERAL ROUTE FROM CARBON DISULFIDE MANGANESE COMPLEXES; X-RAY STRUCTURE OF 1,3-DITHIOL-2-YLIDENEMANGANESE(I) DERIVATIVE
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Chiral carbene-manganese(I) complexes have been synthesized by the cycloaddition of dimethyl acetylenedicarboxylate to the coordinated CS2 ligand in Mn(η2-CS2)(CO)(L)C5H4R (L = P(OMe)3; PMe2Ph; PMe3).Irrespective of the nature of the ligand L, these 1,3-dithiol-2-ylidenemanganese(I) complexes are stable towards isomerisation into heterometallocycles and exhibit low frequency carbonyl absorption bands in the infrared consistent with a strong electron releasing effect of the carbene ligand.The structure of Mn(CS2C2(CO2Me)2)(CO)(P(OMe)3)(C5H5) has been determined by X-ray analysis of a suitable crystal.The molecule shows a carbene carbon-manganese bond C(7)-Mn of length 1.876 Angstroem and a planar carbene which does not adopt the 1,3-dithiolium aromatic-ring geometry but contains a carbon-carbon double bond, C(8)-C(9), of length of 1.341 Angstroem.The CO2Me groups are out of the plane of the carbene ligand and two positions with equal occupancy are found for each oxygen atom O(3) and O(5) belonging to the C=O groups.
- Marouille, J.Y. Le,Lelay, C.,Benoit, A.,Grandjean, D.,Touchard, D.,at al.
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- Unprecedented electrophilic behaviour of tetrathiafulvalenium salts
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Primary tetrathiafulvalenium salts display a diverse and unprecedented reactivity towards nucleophiles.
- Callaghan, Owen,Franck, Xavier,Murphy, John A.
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- An ESR Study of the Radical Cations of Tetrathiafulvalene (TTF) and Electron Donors Containing the TTF Moiety
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Hyperfine data and g factors are reported for the radical cations of tetrathiafulvalene (TTF; 1) and of its derivatives 2-13.From the intense satellite spectra of 1+. - 13+. not only the coupling constants of the 33S isotopes in the TTF moiety could be determined, but also, in favourable cases, those of the 13C isotopes in the central double bond.The former values range from 0.370 (8+.) to 0.470 mT (4+.) and the latter from 0.255 (8+.) to 0.360 mT (4+.) in the radical cations of bis(ethylenedithio)-TTF (8+.) and tetracyano-TTF (4+.).The radical cation of TTF (1+.) exhibits intermediate values, 0.425 for the 33S and 0.285 mT for the 13C isotopes.The spin population in 1+. - 13 +. resides, to a large extent, in the central S2C = CS2 part of the ?-system.It tends to increase (decrease) by substitution with electron-accepting (donating) groups in the 2,3,6,7-positions of TTF.
- Cavara, Luka,Gerson, Fabian,Cowan, Dwaine O.,Lerstrup, Knud
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- A Redox-Active Tetrathiafulvalene [2]Pseudorotaxane: Spectroelectrochemical and Cyclic Voltammetric Studies of the Highly-Reversible Complexation/Decomplexation Process
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The complexation of TTF 2 and cyclobis(paraquat-p-phenylene) 14+ has been studied by cyclic voltammetry and by spectroelectrochemistry: shifts in the redox potentials for the TTF and the 14+ components of 45 and 30 mV, respectively, occur upon complexation. Decomplexation of 2.14+ upon oxidation of the TTF unit to the cation radical species has been monitored by spectroelectrochemistry. The complexation/decomplexation process is highly reversible over at least 10 electrochemical cycles, and this process is accompanied by a color change of the solution from dark green (complexed) to pale brown (uncomplexed) which is clearly visible to the naked eye.
- Devonport, Wayne,Blower, Mark A.,Bryce, Martin R.,Goldenberg, Leonid M.
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- Dimensionality Examination of Cation Radical Salts Based on EDT-TTF (EDT-TTF = Ethylenedithiotetrathiafulvalene)
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Crystal and electronic structures of organic conductors, (EDT-TTF)2X (EDT-TTF = ethylenedithiotetrathiafulvalene; X = PF6, AsF6, TaF6, BF4, ClO4, ReO4, Au(CN)2), have been studied.In all these compounds, the donor molecules exhibit face-to-face stacking.Simple tight-binding band calculations indicate quasi-onedimensional electronic structures.
- Kato, Reizo,Kobayashi, Hayao,Kobayashi, Akiko
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- One-electron Reduction Potentials of Several Electron Acceptor Molecules and Cation Radicals of Donors
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Reversible one-electron reduction potential values of several electron acceptor molecules and cation radicals of donors were estimated by means of the equilibrium constant of electron transfer reaction between ion radicals in acetonitrile solution, and the results were compared with the observed electrochemical data.
- Iida, Yoichi
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- A systematic study of the variation of tetrathiafulvalene (TTF), TTF+ and TTF2+ reaction pathways with water in the presence and absence of light
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The chemistry of the strongly electron donating tetrathiafulvalene (TTF) molecule is exceptionally well known, but detailed knowledge of the chemistry of its technologically important one (TTF+) and two (TTF2+) electron oxidised redox partners is limited. In this paper, the different pathways that apply to the reaction of TTF, TTF+ and TTF2+ with water have been identified in the absence and presence of light. On the basis of data obtained by transient and steady state voltammetric methods in CH3CN (0.1 M Bu4NPF6) containing 10% (v/v) H2O, TTF is shown to participate in an acid base equilibrium reaction with HTTF+, with H2O acting as the proton donor. In contrast, TTF+ generated by one electron bulk oxidative electrolysis of TTF remains unprotonated and fully stable in the presence of 10% H2O in the dark. However, when this cation radical is exposed to white or blue (λ = 425 nm) light, TTF+ is photoreduced to TTF, with oxidation of water to give oxygen (detected by a Clark electrode) and protons that react with TTF to give HTTF+ as the counter reaction. Again emphasising important reaction pathway differences associated with each redox level, TTF2+ generated by bulk two electron oxidative electrolysis of TTF reacts rapidly with water, even in the dark, to give TTF+, protons, HTTF+ and oxygen as the products.
- Adeel, Shaimaa M.,Li, Qi,Nafady, Ayman,Zhao, Chuan,Siriwardana, Amal I.,Bond, Alan M.,Martin, Lisandra L.
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- Azulene-based tetrathiafulvalenes: Preparation and their electron-donating ability
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The condensation reaction of dithiocarbonates derived from azuleno- and guaiazulenopentathiepin with vinylene trithiocarbonate and the ethylenedithio derivative in triethyl phosphite afforded azulene-based tetrathiafulvalenes [Az-TTF, Az-(EDT)TTF, GAz-TTF and GAz-(EDT)TTF], respectively. The vinylene derivatives (Az-TTF and GAz-TTF) showed slightly higher electron-donating ability than the corresponding ethylenedithio ones [Az-(EDT)TTF and GAz-(EDT)TTF] by CV measurement. GAz-TTFs produced charge transfer complexes with tetracyanoquinodimethane, respectively.
- Sato, Ohki,Saito, Takahito,Aoki, Masami,Sakai, Atsushi
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p. 1254 - 1260
(2019/11/14)
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- Metal cation binding to acetylenic tetrathiafulvalene–pyridine conjugates: affinity tuned by preorganization and cavity size
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A series of three structurally related mono-, bidentate and macrocyclic TTF-pyridine hosts were prepared and titrated with several metal cations including Ag+and Pb2+and studied using NMR- and UV–vis spectroscopy and cyclic voltammetry. For Ag+, we found an eightfold increase in binding affinity between the bidentate and macrocyclic host and conversely, for Pb2+, a 100-fold drop. Density functional theory (DFT) calculations support the increased binding affinity for Ag+is due to an N?N distance for the uncomplexed macrocycle very much suited for binding of Ag+but being too small for Pb2+. The bidentate host, on the other hand, is of a suitable size for Pb2+.
- Broman, S?ren Lindb?k,Andersen, Cecilie Lindholm,Jevric, Martyn,Tortzen, Christian Gregers,Hammerich, Ole,Nielsen, Mogens Br?ndsted
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supporting information
p. 5831 - 5842
(2016/09/07)
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- Charging a Li-O2 battery using a redox mediator
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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 Li 2O2 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 Li2O 2, which results in the regeneration of TTF. The mediator acts as an electron-hole transfer agent that permits efficient oxidation of solid Li 2O2. The cell with the mediator demonstrated 100 charge/discharge cycles.
- Chen, Yuhui,Freunberger, Stefan A.,Peng, Zhangquan,Fontaine, Olivier,Bruce, Peter G.
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p. 489 - 494
(2013/07/25)
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- SUPRAMOLECULAR HANDCUFFS IN POLYMERIC ARCHITECTURE
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This invention pertains generally to supramolecular polymers comprising a polymeric molecule linked to a first CB[8] guest molecule and an attachment compound linked to a second CB[8] guest molecule, wherein the first and second CB[8] guest molecules form a ternary host-guest complex with a CB[8] molecule which non-covalently links the polymeric molecule and the attachment compound in a supramolecular polymer. These polymers are useful as vehicles for delivery of a therapeutic compound for use in a method of treatment of the human or animal body, in particular for use in a method of delivering the therapeutic compound to a target site in an individual. The invention also provides methods for the preparation of the supramolecular polymers.
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- Synthesis and reactivity of silylated tetrathiafulvalenes
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Novel organosilylated tetrathiafulvalenes (TTFs) possessing Si-H or Si-Si bonds have been synthesised. The crystal structures of several derivatives have been determined by X-ray diffraction, including that of dimeric (Si 2Me4)(TTF)2 (11) incorporating a diatomic SiMe2-SiMe2 linker. Cyclic voltammetry measurements in all cases show two oxidation waves. DFT calculations were performed to rationalize the absence of an electronic communication between the two TTF moieties of 11 through the disilanyl spacer. The reactivity of the Si-H bond has been exploited to prepare the dinuclear complex [{Ru(CO)4}2{μ- (Me2Si)4TTF}] (14), starting from Ru3(CO) 12 and TTF(SiMe2H)4 (1). Treatment of 14 with 2 equiv. of PPh3 or dppm results in selective substitution of a CO ligand trans to a SiMe2 group to afford mer-[{Ru(PPh 3)(CO)3}2{μ-(Me2Si) 4TTF}] (13) and mer-[{Ru(CO)3}2(η 1-dppm){μ-(Me2Si)4TTF}] (16). Attempts to transform the Si-H bonds of some TTF(SiMe2H)n (n = 1, 2) into Si-O functions using stoichiometric amounts of water in the presence of tris(dibenzylideneacetone)dipalladium(0) were unsuccessful. Quantitative cleavage of the CTTF-Si bond was observed instead of formation of TTF-based-siloxanes. Essays of catalytic bis-silylation of phenylacetylene with 11 and TTF(SiMe2-SiMe3) (9) in the presence of Pd(OAc)2/1,1,3,3-tetramethylbutylisocyanide failed. Again, cleavage of the CTTF-Si bond was noticed.
- Hameau, Aurelien,Guyon, Fabrice,Knorr, Michael,Daeschlein, Christian,Strohmann, Carsten,Avarvari, Narcis
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scheme or table
p. 4866 - 4876
(2009/02/03)
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- S-position isomers of BEDT-TTF and EDT-TTF: Synthesis and influence of outer sulfur atoms on the electrochemical properties and crystallographic network of related organic metals
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The synthesis and characterization of new modified tetrathiafulvalenes (TTF), the S-position isomers of BEDT-TTF and EDT-TTF, are described. The synthetic strategy presented in this work is based on an efficient and unprecedented two-step sequence for the conversion of a vicinal bis(hydroxymethyl) functionality into a disulfide ring. Different routes are discussed in terms of efficiency for the synthesis of the symmetric S-position isomer of BEDT-TTF and that of EDT-TTF. Their electrochemical properties are combined with data obtained from UV/Vis spectroscopy and orbital calculations, and the electronic influence of peripheral sulfur atoms on the neutral and oxidized species is discussed. The introduction of these outer sulfur atoms at the periphery of the TTF core gives rise to specific intermolecular S ··· S interactions in the corresponding organic materials. Crystallographic studies of radical cation salts synthesized upon electrocrystallization clearly showed that the network obtained is dictated by the outer sulfur atoms, which are responsible for a characteristic and unprecedented windmill array.
- Hudhomme, Pietrick,Le Moustarder, Soazig,Durand, Christophe,Gallego-Planas, Nuria,Mercier, Nicolas,Blanchard, Philippe,Levillain, Eric,Allain, Magali,Gorgues, Alain,Riou, Amedee
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p. 5070 - 5083
(2007/10/03)
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- On the ring-contraction of 1,4-dithiins to 1,3-dithiole derivatives
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The effect of different factors (pKa of the base, nature of the counterion and dissociation of the ion pairs) on the course of the base-induced rearrangement of 1,4-dithiins to 1,3-dithiole derivatives is discussed. Ab initio calculations account for the driving force of these isomerisations.
- Andreu, Raquel,Garín, Javier,Orduna, Jesús,Royo, José M.
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p. 875 - 877
(2007/10/03)
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- An expedient, cost effective large scale synthesis of tetrathiafulvalene
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TTF is synthesized (85% yield) in two steps from 4,5-bis(benzoylthio)-1,3-dithiole-2-thione and isolated in high purity without the use of chromatography.
- Meline, Ronald L.,Elsenbaumer, Ronald L.
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p. 2467 - 2469
(2007/10/03)
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- In Situ Electrochemical EPR Studies of Charge Transfer across the Liquid/Liquid Interface
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The in situ measurement of EPR spectra of radical ions generated at the polarized liquid/liquid interface is described in relation to the 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrachloro-p-benzoquinone (TCBQ), and 2,3,5,6-tetrafluoro-p-benzoquinone (TFBQ) radical anions and the tetrathiafulvalene (TTF) radical cation. TCNQ and TTF were chosen as model compounds with which to quantify the performance of a novel liquid/ liquid electrochemical EPR cell. The anion radical of TCNQ and the cation radical of TTF in 1,2-dichloroethane (DCE) were produced at the water interface by electron transfer from/to the aqueous-phase ferricyanide/ferrocyanide redox couple by applying a potential difference between the two phases with a four-electrode potentiostat. The EPR signal intensity (at constant magnetic field) of the resultant organic radicals was monitored during potential step experiments which indicated that the EPR data could be modeled in terms of diffusional transport. TCBQ and TFBQ were chosen as compounds to model the electron transfer behavior of biologically important quinones at the oil/water interface. The EPR and voltammetric data obtained from TCBQ/TCBQ-· and TFBQ/ TFBQ-· indicated unambiguously that the two semiquinones are stable at the DCE/water interface and do not undergo immediate protonation.
- Webster, Richard D.,Dryfe, Robert A. W.,Coles, Barry A.,Compton, Richard G.
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p. 792 - 800
(2007/10/03)
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- Electron Transfer from Tetrathiafulvalenes to Photoexcited C70 Studied by Observing Transient Absorption in the Near-IR Region
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The photoinduced electron transfer between C70 and tetrathiafulvalene or bis(ethylenedithio)tetrathiafulvalene in polar and nonpolar solvents and their mixture has been investigated by nanosecond laser photolysis/transient absorption spectroscopy in the visible and near-IR regions.The transient absorption bands of the triplet state of C70 observed in polar solvents decayed upon addition of tetrathiafulvalenes accompanied by the appearance of the transient absorption bands of the radical anion of C70.In benzene, the quenching of the triplet state of C70 was observed without the appearance of the radical anion of C70 within a nanosecond laser pulse, suggesting a collisional quenching of the triplet state of C70 with tetrathiafulvalenes.The quantum yield for the formation of the radical anion via the triplet state of C70 was about 1 for tetrathiafulvalene in benzonitrile.The quantum yield decreased in less polar solvents.The back electron transfer rates were also evaluated in polar solvents.
- Alam, Maksudul M.,Watanabe, Akira,Ito, Osamu
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p. 1833 - 1838
(2007/10/03)
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- Direct syntheses of tetrathiafulvalene and bis- (ethylenedithio)tetrathiafulvalene by a non-coupling route from 1,4,5,8- tetrathianaphthalene
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1,4,5,8-Tetrathianaphthalene (2, TTN; 1,4,5,8-tetrathiatetralin) has been synthesized in one step from 4,5-bis(benzoylthio)-1,3-dithiole-2-thione (1) and cis-dichloroethylene in high yield. TTN (2) is readily converted into tetrathiafulvalene (3, TTF) upon tetralithiation or bis(ethylenedithio)tetrathiafulvalene (4, BEDT-TTF) upon tetralithiation, sulfur insertion into the carbon lithium bond pairs and subsequent capping of the reactive intermediate with 1,2-dibromoethane. The rearrangement of TTN allows for a facile synthesis of TTF and a novel non-coupling route to BEDT- TTF.
- Meline, Ronald L.,Elsenbaumer, Ronald L.
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p. 617 - 619
(2007/10/03)
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- Synthesis and some properties of bis- and tetrakis(triphenylstannyl) tetrathiafulvalenes and tetraiodotetrathiafulvalene
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Bis- and tetrakis(triphenylstannyl)tetrathiafulvalenes were prepared from the corresponding lithio-derivatives and chlorotriphenyltin, and their structures were determined by X-ray analysis. Their absorption maxima in the electronic spectrum showed a bathochromic shift. Their redox potentials shifted only a little to a lower region. The charge-transfer complex of the tetra-substituted derivative with TCNQ was isolated. Bis(trimethylstannyl)tetrathiafulvalene did not react with (η-Cp)(CO)2FeI and the reaction with (COD)PtCl2, followed by addition of tributylphosphine, gave a complex mixture, from which (C2H2S2)Pt(PBu3)2 was isolated in a low yield. The structure was confirmed by X-ray diffraction. A convenient preparation of tetrathiafulvalene and tetraiodotetrathiafulvalene is also reported.
- Sato, Masaru,Sensui, Masa-Aki
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- Highly extended, planar and sulfur-rich tetrathiafulvalene derivatives: Towards an increased dimensionality of organic metals
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Highly extended π-donors 1-3 have been obtained through twofold or fourfold Wittig olefinations of polyformyl tetrathiafulvalenes with P-ylids bearing the 1,3-dithiol-2-ylidene moiety. Their powerful π-donor properties as well as their ability to generate cation-radical salts of mixed valency have been evaluated by both classical and thin layer cyclic voltammetry. Such extended π-donors prove to be planar in the neutral state, with very short intramolecular S...S distances, as demonstrated by the X-ray diffraction study of the model compound 16b. Such extended sulfur-rich tetrathiafulvalene derivatives are prone to generate highly dimensional materials as demonstrated in the case of the 3a.ClO4 cation-radical salt which presents a unique type of two-dimensional network in the solid-state. Elsevier,.
- Salle, Marc,Gorgues, Alain,Jubault, Michel,Boubekeur, Kamal,Batail, Patrick,Carlier, Roger
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p. 417 - 426
(2007/10/03)
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- Tetrathiafulvalene: a catalyst for sequential radical-polar reactions
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The reaction between tetrathiafulvalene (TTF) and suitable arenediazonium salts leads to products arising from an ordered sequence of reactions featuring electron transfer, loss of nitrogen, radical cyclisation and nucleophilic substitution.The tetrathiafulvalenium salt 6 is shown to be an intermediate in the reaction, with substitution of TTF occuring via an SN1 mechanism.The reactions are catalytic in TTF and the final substitution can be achieved by several nucleophiles.Extension of the reaction to the synthesis of bi- and tricyclic ring systems has been investigated.
- Fletcher, Rodney J.,Lampard, Christopher,Murphy, John A.,Lewis, Norman
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p. 623 - 634
(2007/10/02)
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- Synthesis of 4,5-bis- and 4,4',5,5',-tetrakis(2-hydroxyethylthio)tetrathiafulvalene: The assembly of tris- and pentakis(tetrathiafulvalene) macromolecules
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Efficient syntheses are reported of the novel pentakis- and tris(tetrathiafulvalene) derivatives 11 and 12, respectively, by esterification of tetraol and diol derivatives 8 and 10 with TTF-carbonyl chloride.
- Marshallsay,Hansen,Moore,Bryce,Becher
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p. 926 - 930
(2007/10/02)
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- SYNTHESES ET CARACTERISATION DES DERIVES METHYLES DU TETRATHIAFULVALENE; NOUVELLE VOIE D'ACCES AU TETRATHIAFULVALENE
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We propose an improved general method for the synthesis of tetrathiafulvalene and its methylated derivatives.TTF is obtained in a five steps preparation offering a high Overall yield. Concerning the unsymmetrically methylated tetrathiafulvalenes, four different procedures are analysed.It is shown the best routes to prepare trimethyltetrathiafulvalene are a WITTIG type reaction, and a selective synthesis based on a WITTIG-HORNER reaction.The monomethyltetrathiafulvalene has been isolated in a 96percent state of purity.
- Mora, Henri,Fabre, Jean-Marc,Giral, Louis,Montginoul, Claude
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p. 137 - 146
(2007/10/02)
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- A Facile Preparation of Tetrathiafulvalenes having Alkylthio Groups from 1,3-Dithiole-2-thiones using a High-pressure Reaction
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Tetrathiofulvalenes such as bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) having alkylthio substituents have been prepared in good yields by direct desulphurization of 1,3-dithiole-2-thiones with trimethyl phosphite under high pressure.
- Yamashita, Yoshiro,Tomura, Masaaki,Tanaka, Shoji
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p. 3358 - 3359
(2007/10/02)
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- Unsymmetrically Substituted Ethylenedioxytetrathiafulvalenes
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Seven new electron donors, 4,5-ethylenedioxytetrathiafulvalenes where 4',5'-substituents are trimethylenedithio, ethylenedithio, methylenedithio, 2-oxatrimethylenedithio, methylthio, hydrogen and methyl carboxylate, are prepared, and their electrochemical properties are investigated.
- Mori, Takehiko,Inokuchi, Hiroo,Kini, Aravinda M.,Williams, Jack M.
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p. 1279 - 1282
(2007/10/02)
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- Homogeneous and Heterogeneous Electron Transfer Rates of the Tetrathiafulvalene-System
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Using ESR spectroscopy and cyclic voltammetry the rate constants of homogeneous and heterogeneous electron self exchange in the system TTF/TTF+radical were measured at different temperatures in solvents of different polarities and relaxation times (TTF = tetrathiofulvalene = 2-(1,3-dithiol-2-ylidene)-1,3-dithiol).The rate constants were expressed by the preequilibrium encounter model for adiabatic processes.For both reactions the results are discussed in terms of Marcus's theory for the reorganization of ellipsoidal molecules in the overdamped relaxation case.From the experiments the geometric term g = 1/r - 1/d'was derived and compared with model calculations ( r = mean molecular radius, d'= formal distance between the reactants resp. reactant and image charge).Approximately interaction energies of the reactants (in the homogeneous case) and double layer correction (in the heterogeneous case) can be neglected.Preexponential and activation terms of the rate constants agree satisfactorily with the theory. g(het) is about the tenfold of g(hom).This is explained by an increased d' caused by strong adsorption of the counterions of the supporting electrolyte on the electrode.
- Grampp, Guenter,Kapturkiewicz, Andrej,Jaenicke, Walther
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p. 439 - 447
(2007/10/02)
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- SYNTHESIS AND ELECTROCHEMICAL BEHAVIOR OF 1,4-DITHIIN RING CONDENSED SYSTEMS
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Alkylthio-substituted derivatives of 1,4-dithiin (1a), 1,4,5,8-tetrathianaphthalene (2a), 1,4,5,6,9,10-hexathiaanthracene (3a) and 1,4,5,6,7,10,11,12-octathianaphthacene (4a) are synthesized by Diels-Alder reaction of cis-1,2-dialkylthioethylenes or 2a with dimethyl tetrathiooxalate (6) and the successive dehydrogenation with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ).The electrochemical behavior of the new compounds(1b, 2b, 3b and 4b) and 2a is investigated by cyclic voltammetry.The skeletal rearrangement of 2a to tetrathiafulvalene (TTF) via the dication state, is found to occur by electrochemical or chemical means.
- Sugimoto, Toyonari,Sugimoto, Iwao,Kawashima, Akihiko,Yamamoto, Yukishi,Misaki, Yohji,Yoshida, Zen-ichi
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- BASE-CATALYZED HALOGEN DANCE OF 2-BROMOTETRATHIAFULVALENE
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Halogenotetrathiafulvalenes were prepared by treating tetrathiafulvalene with lithium diisopropylamide (LDA) and then with halogenating agents.Treatment of 2-bromotetrathiafulvalene with LDA results in the bromine dance which affords tetrathiafulvalene, 2-bromotetrathiafulvalene, three positional isomers of dibromotetrathiafulvalene, and 2,3,6-tribromotetrathiafulvalene.
- Nakayama, Juzo,Toyoda, Nagatoshi,Hoshino, Masamatsu
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p. 1145 - 1150
(2007/10/02)
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- INTERNAL SALTS OF THE RADICAL-CATIONS OF TETRATHIAFULVALENECARBOXYLIC ACIDS. SYNTHESIS AND PROPERTIES
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Internal salts of the radical-cations of tetrathiafulvalenecarboxylic acids (IIIa-c) were obtained by the oxidation of the salts (Ia-c) with ferricinium tetrafluoroborate or potassium ferricyanide or of the tetrathiafulvalenecarboxylic acids (IIa-c) themselves with hydrogen peroxide.The characteristics of the products were investigated, and a complex with tetrathiafulvalene was obtained.
- Kreitsberga, Ya. N.,Neiland, O. Ya.
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p. 2131 - 2134
(2007/10/02)
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- NEW MOLECULAR CONDUCTORS: VARIATION ON THE BEDTTTF SKELETON
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New organic conductors obtained by modification of the BEDTTTF molecule are presented.The synthesis of these compounds is detailed and some physical properties are given.
- Laversanne, R.,Dupart, E.,Delhaes, P.
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p. 179 - 190
(2007/10/02)
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- Tetrathiafulvalenes. XXII. - Redox- and Spectroscopic Properties of Tetratiafulvalenes (TTF) and Tetraselenafulvalenes (TSF) and their Mono- and Dications
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The polarographic oxidation potential of TTF is decreased by alkyl- and increased by aryl-substituents.The oxidation potentials of arylated TTF can be correlated with ?(+)-constants (ρ = 0,1).TSF are weaker donors than the respective TTF.Alkyl substitution at TTF causes a bathochromic shift and aryl substitution a hypsochromic shift of the longest wavelength absorption band.In the mono- and dications of TTF a bathochromic shift of this absorption band is observed by alkyl- as well as aryl-substituents which is especially pronounced, when the molecule is planar.
- Schukat, G.,Fanghaenel, E.
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p. 767 - 774
(2007/10/02)
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- Dimer Cation Formation in Anionic Microemulsion Media. Duroquinone-Sensitized Photooxidation of 2,6-Dimethylnaphthalene and Tetrathiafulvalene
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Flash photolysis studies using a ruby laser (λ=347 nm, doubled line) were performed on the systems duroquinone (DQ)/2,6-dimethylnaphthalane (DMN) and DQ/tetrathiafulvalene (TTF) principally in sodium hexadecyl sulfate (SCS) microemulsion media.Electron transfer from both DMN and TTF to triplet duroquinone with efficient charge separation to produce the product cations and anion was observed in these media.Identical experiments performed in homogeneous media demonstrated electron transfer but with less efficient charge separation and consequently lower product ion yields.Dimer cation formation of both DMN and TTF, i.e., (DMN)2+ and (TTF)2+, in the anionic microemulsion media was readily detected.The formation of (TTF)2+ was reverified by pulse radiolysis experiments.Although tetrathiafulvalene stacks easily in organic conducting salts and thus should have no difficulty in obtaining the supposed sandwichlike configuration of the dimer, no previous reports announce its detection.Dimer cation formation of aromatic compounds in microemulsion media is unique in itself since the majority of previous studies of this type involved γ irradiation of substrate solubilized in glassy alkane matrices at low temperatures (77 K).The dimer formation constant for DMN was evaluated graphically as K=4.76*102.
- Graetzel, Carole K.,Kira, Akira,Jirousek, Marie,Graetzel, Michael
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p. 3983 - 3988
(2007/10/02)
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- Electron Transfer Reaction between Δ2,2'-Bi-1,3-dithiole (TTF) and 7,7,8,8-Tetracyanoquinodimethane (TCNQ). Electron Donating Property of TTF
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The reaction between Δ2.2'-bi-1,3-dithiole (TTF) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in acetonitrile solution, TTF + TCNQ = TTF +. =TCNQ -., was analyzed spectrophotometrically.The thermodynamical data of chemical equilibrium were determined to be K=(2.8 +/- 0.1)*10-3 at 11 deg C, ΔH=-6.7 +/-1.3 kJ mol -1 and Σ=-72.8 +/- 17 JK-1mol-1.The reaction-rate study of the equilibrium in several solvents was also made by temperature-jump technique.The difference in the electron-donating properties between TTF and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) is discussed by comparing the results with those of the reaction between TMPD and TCNQ.
- Yamagishi, Akihiko,Iida, Yoichi
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p. 1340 - 1343
(2007/10/02)
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- Organic Metals: a New Synthetic Route to Tetrathiafulvalenes
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We report here a new synthetic route to tetrathiafulvalenes in asimple one-step synthesis from 2-thioxo-1,3-dithioles.
- Coustumer, Gerard Le,Mollier, Yves
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