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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Received: 23 March 2012; in revised form: 24 April 2012 / Accepted: 24 April 2012 / Published: 9 May 2012
(This article belongs to the Special Issue Molecular Conductors)
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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
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MDPI and ACS Style

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.

AMA Style

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(2):393-412.

Chicago/Turabian Style

Furuta, Keisuke; Kohno, Shuhei; Shirahata, Takashi; Yamasaki, Koya; Hino, Shojun; Misaki, Yohji. 2012. "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 2, no. 2: 393-412.

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