35079-56-2Relevant articles and documents
A systematic study of the variation of tetrathiafulvalene (TTF), TTF+ and TTF2+ reaction pathways with water in the presence and absence of light
Adeel, Shaimaa M.,Li, Qi,Nafady, Ayman,Zhao, Chuan,Siriwardana, Amal I.,Bond, Alan M.,Martin, Lisandra L.
, p. 49789 - 49795 (2015/01/09)
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.
In Situ Electrochemical EPR Studies of Charge Transfer across the Liquid/Liquid Interface
Webster, Richard D.,Dryfe, Robert A. W.,Coles, Barry A.,Compton, Richard G.
, p. 792 - 800 (2007/10/03)
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.
An ESR Study of the Radical Cations of Tetrathiafulvalene (TTF) and Electron Donors Containing the TTF Moiety
Cavara, Luka,Gerson, Fabian,Cowan, Dwaine O.,Lerstrup, Knud
, p. 141 - 152 (2007/10/02)
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.
