Crystalline patterns and band structure dimensionality in a series of conducting hybrids associating amide-functionalized EDT-TTF π-donors with the isosteric octahedral anions [FeNO(CN)<inf>5</inf>]<sup>2-</sup> and [M(CN) <inf>6</inf>]<sup>3-</sup> (M = Co, Fe)

L. V. Zorina, S. S. Khasanov, S. V. Simonov, R. P. Shibaeva, L. A. Kushch, L. I. Buravov, E. B. Yagubskii, S. Baudron, C. Mézière, P. Batail, E. Canadell, P. Auban-Senzier

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    4 Citations (Scopus)

    Abstract

    Four new radical cation salts based on the amide functionalized EDT-TTF organic donors EDT-TTF-CONH2 (D1) and EDT-TTF-(CONH2) 2 (D2), α′-(D1)4[FeNO(CN)5] (1), α′-(D1)4[Co(CN)6] (2), β-(D1) 6[Fe(CN)6] (3) and (D2)4[FeNO(CN) 5]NB (4), have been synthesized and characterized by X-ray single crystal diffraction experiments, band structure calculations and electrical resistivity measurements. Functionalized organic donors are remarkable for the ability to form cation⋯cation and cation⋯anion type hydrogen bonds which can effectively direct the crystal architecture of molecular conductors. The structural analysis reveals a well-developed hydrogen bond network in the crystals investigated. (D1)2-dimers or (D2)n-extended zigzag chains of donors connected through functional groups are found to be stable structural motifs in 1-4. Remarkably, salts 1 and 2 are isostructural despite the presence of anions of different charge (-2 and -3, respectively) and the inherent difference in the degree of charge transfer has a clear effect on the transport properties: σRT(2)/σRT(1) = 300. Salt 3 differs from 1 and 2 both in the stoichiometry and packing of the conducting organic layer. Crystals of 4 exhibit a superstructure with the incommensurate vector q = ±(0.5, 0.3, 0.2). © 2005 Elsevier B.V. All rights reserved.
    Original languageEnglish
    Pages (from-to)527-538
    JournalSynthetic Metals
    Volume155
    Issue number3
    DOIs
    Publication statusPublished - 15 Dec 2005

    Keywords

    • Band structure
    • Low-dimensional organic conductors
    • X-ray diffraction

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