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

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 1‑4 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.
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Submitted on : Wednesday, July 5, 2017 - 3:17:48 PM
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Samia Benmansour, Mathieu Marchivie, Smail Triki, Carlos J. Gómez-García. Polymorphism and Metallic Behavior in BEDT-TTF Radical Salts with Polycyano Anions. Liquid Crystals, Taylor & Francis, 2012, 2 (4), pp.306 - 326. ⟨10.3390/cryst2020306⟩. ⟨hal-01556779⟩

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