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Crystals 2012, 2(2), 306-326; doi:10.3390/cryst2020306

Polymorphism and Metallic Behavior in BEDT-TTF Radical Salts with Polycyano Anions

1
Institute of Molecular Science (ICMol), University of Valencia, 46980 Paterna, Valencia, Spain
2
European University of Brittany (University of Brest), UMR CNRS 6521, 6 Av. V. Le Gorgeu, C.S. 93837, 29238 Brest, France
3
University of Bordeaux, CNRS FRE 3396, 146, rue Léo Saignat, 33076 Bordeaux, France
*
Author to whom correspondence should be addressed.
Received: 27 March 2012 / Revised: 12 April 2012 / Accepted: 13 April 2012 / Published: 23 April 2012
(This article belongs to the Special Issue Molecular Conductors)
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Abstract

Up to five different crystalline radical salts have been prepared with the organic donor BEDT-TTF and three different polynitrile anions. With the polynitrile dianion tcpd2− (=C[C(CN)2]32−), two closely related radical salts: α'-(ET)4tcpd·THF (1) (THF = tetrahydrofurane) and α'-(ET)4tcpd·H2O (2) have been prepared, depending on the solvent used in the synthesis. With the mono-anion tcnoetOH (=[(NC)2CC(OCH2CH2OH)C(CN)2]) two polymorphs with similar physical properties but different crystal packings have been synthesized: θ-(ET)2(tcnoetOH) (3) and β''-(ET)2(tcnoetOH) (4). Finally, with the mono-anion tcnoprOH (=[(NC)2CC(OCH2CH2CH2OH)C(CN)2]) we have prepared a metallic radical salt: β''-(ET)2(tcnoprOH)(CH2Cl2CH3Cl)0.5 (5). Salts 14 are semiconductors with high room temperature conductivities and activation energies in the range 0.1–0.5 eV, whereas salt 5 is metallic down to 0.4 K although it does not show any superconducting transition above this temperature.
Keywords: bis(ethylenedithio)tetrathiafulvalene; polycyano anions; molecular conductors; synthetic metals bis(ethylenedithio)tetrathiafulvalene; polycyano anions; molecular conductors; synthetic metals
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Benmansour, S.; Marchivie, M.; Triki, S.; Gómez-García, C.J. Polymorphism and Metallic Behavior in BEDT-TTF Radical Salts with Polycyano Anions. Crystals 2012, 2, 306-326.

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