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

doi:10.3390/cryst2020393

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

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

Keisuke Furuta, Shuhei Kohno, Takashi Shirahata * , Koya Yamasaki, Shojun Hino and Yohji Misaki

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; in revised form: 24 April 2012 / Accepted: 24 April 2012 / Published: 9 May 2012

(This article belongs to the Special Issue Molecular Conductors)

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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 (E_a = 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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