Tetramethyl-Bis(ethylenedithio)-Tetrathiafulvalene (TM-BEDT-TTF) Revisited: Crystal Structures, Chiroptical Properties, Theoretical Calculations, and a Complete Series of Conducting Radical Cation Salts - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Chirality Année : 2013

Tetramethyl-Bis(ethylenedithio)-Tetrathiafulvalene (TM-BEDT-TTF) Revisited: Crystal Structures, Chiroptical Properties, Theoretical Calculations, and a Complete Series of Conducting Radical Cation Salts

Flavia Pop
S. Laroussi
  • Fonction : Auteur
Thomas Cauchy
Carlos Gómez-García
  • Fonction : Auteur
John-D. Wallis
  • Fonction : Auteur
Narcis Avarvari

Résumé

The (S,S,S,S) and (R,R,R,R) enantiomers of tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) show equatorial conformation for the four methyl groups in the solid state, according to the single-crystal X-ray analyses. Theoretical calculations at the Density Functional Theory (DFT) and time-dependent (TD) DFT levels indicate higher gas phase stability for the axial conformer than the equatorial one by 1.25kcal center dot mole-1 and allow the assignment of the UV-vis and circular dichroism transitions. A complete series of radical cation salts of 1:1 stoichiometry with the triiodide anion I3- was obtained by electrocrystallization of both enantiopure and racemic forms of the donor. In the packing the donors are organized in dimers that further interact through S center dot center dot center dot S intermolecular contacts and the triiodide anions lie parallel to pairs of oxidized donors. The conductivity of the racemate, which adopts the same, but disordered, structural type, is considerably lower, with much higher activation energy. Chirality 25:466-474, 2013.

Domaines

Chimie

Dates et versions

hal-01390657 , version 1 (02-11-2016)

Identifiants

Citer

Flavia Pop, S. Laroussi, Thomas Cauchy, Carlos Gómez-García, John-D. Wallis, et al.. Tetramethyl-Bis(ethylenedithio)-Tetrathiafulvalene (TM-BEDT-TTF) Revisited: Crystal Structures, Chiroptical Properties, Theoretical Calculations, and a Complete Series of Conducting Radical Cation Salts. Chirality, 2013, 25 (8), pp.466-474. ⟨10.1002/chir.22210⟩. ⟨hal-01390657⟩
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