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Crystals 2012, 2(2), 393-412; doi:10.3390/cryst2020393
Article

Synthesis and Properties of 2-Alkylidene-1,3-dithiolo[4,5-d]-4,5-ethylenediselenotetrathiafulvalene Derivatives and Crystal Structures of Their Cation Radical Salts

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Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577, Japan
* Author to whom correspondence should be addressed.
Received: 23 March 2012 / Revised: 24 April 2012 / Accepted: 24 April 2012 / Published: 9 May 2012
(This article belongs to the Special Issue Molecular Conductors)

Abstract

Tetrathiafulvalene derivatives condensed with 2-alkylidene-1,3-dithiole moiety, MeDTES (2-isopropylidene-1,3-dithiolo[4,5-d]-4,5-ethylenediselenotetrathiafulvalene), EtDTES (2-(pentan-3-ylidene)-1,3-dithiolo[4,5-d]-4,5-ethylenediselenotetrathiafulvalene), and CPDTES (2-cyclopentanylidene-1,3-dithiolo[4,5-d]-4,5-ethylenediselenotetrathiafulvalene) have been synthesized. Crystal structure analysis of MeDTES salts with Au(CN)4, ReO4, and I3 and a CPDTES salt with I3 reveals that the donor−anion ratios of all salts are 1:1. Band calculation of (MeDTES)[Au(CN)4] suggests a quasi-one-dimensional Fermi surface that could be the result of the uniform stack of donor molecules. In spite of this stacking, the salt is a Mott insulator because of a large on-site Coulomb interaction U. (MeDTES)(ReO4)(H2O)0.5 possesses Fermi points and exhibits semiconducting behavior with small activation energy (Ea = 0.058 eV). I3 ions form disordered infinite chain in (MeDTES)(I3)(DCE)0.25, but those in (CPDTES)(I3) exist as discrete ions. They show low conductivity (10−4−10−2 S cm−1) at room temperature and the band calculation suggests that they are band insulator.
Keywords: molecular conductors; tetrathiafulvalene derivatives; cation radical salts; crystal structure; band calculation molecular conductors; tetrathiafulvalene derivatives; cation radical salts; crystal structure; band calculation
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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Furuta, K.; Kohno, S.; Shirahata, T.; Yamasaki, K.; Hino, S.; Misaki, Y. Synthesis and Properties of 2-Alkylidene-1,3-dithiolo[4,5-d]-4,5-ethylenediselenotetrathiafulvalene Derivatives and Crystal Structures of Their Cation Radical Salts. Crystals 2012, 2, 393-412.

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