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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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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
This is an open access article distributed under the Creative Commons Attribution License (CC BY) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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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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