Structural Diversity and Physical Properties of Paramagnetic Molecular Conductors Based on Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and the Tris(chloranilato)ferrate(III) Complex

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• 作者：Matteo Atzori ; Flavia Pop ; Pascale Auban-Senzier ; Carlos J. G贸mez-Garc铆a ; Enric Canadell ; Flavia Artizzu ; Angela Serpe ; Paola Deplano ; Narcis Avarvari ; Maria Laura Mercuri
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：July 7, 2014
• 年：2014
• 卷：53
• 期：13
• 页码：7028-7039
• 全文大小：794K
• ISSN：1520-510X

文摘

Electrocrystallization of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) in the presence of the tris(chloranilato)ferrate(III) [Fe(Cl₂An)₃]^{3鈥?/sup> paramagnetic chiral anion in different stoichiometric ratios and solvent mixtures afforded three different hybrid systems formulated as [BEDT-TTF]₃[Fe(Cl₂An)₃]路3CH₂Cl₂路H₂O (1), 未-[BEDT-TTF]₅[Fe(Cl₂An)₃]路4H₂O (2), and 伪鈥?[BEDT-TTF]₁₈[Fe(Cl₂An)₃]₃路3CH₂Cl₂路6H₂O (3). Compound 1 presents an unusual structure without the typical alternating organic and inorganic layers, whereas compounds 2 and 3 show a segregated organic鈥搃norganic crystal structure where layers formed by 螞 and 螖 enantiomers of the paramagnetic complex, together with dicationic BEDT-TTF dimers, alternate with layers where the donor molecules are arranged in the 未 (2) and 伪鈥?(3) packing motifs. Compound 1 behaves as a semiconductor with a much lower conductivity due to the not-layered structure and strong dimerization between the fully oxidized donors, whereas 2 and 3 show semiconducting behaviors with high room-temperature conductivities of ca. 2 S cm鈥? and 8 S cm鈥?, respectively. The magnetic properties are dominated by the paramagnetic S = 5/2 [Fe(Cl₂An)₃]3鈥?/sup> anions whose high-spin character is confirmed by electron paramagnetic resonance and magnetic susceptibility measurements. The correlation between crystal structure and conductivity behavior was studied by means of tight-binding band structure calculations, which support the observed conducting properties.}