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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)5]2− and [M(CN)6]3− (M=Co, Fe)

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).
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https://hal.univ-angers.fr/hal-02542170
Contributeur : Cécile Meziere <>
Soumis le : mardi 14 avril 2020 - 15:08:47
Dernière modification le : mercredi 14 octobre 2020 - 03:59:30

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L.V. Zorina, S.S. Khasanov, S.V. Simonov, R.P. Shibaeva, L.A. Kushch, et al.. 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)5]2− and [M(CN)6]3− (M=Co, Fe). Synthetic Metals, Elsevier, 2005, 155 (3), pp.527-538. ⟨10.1016/j.synthmet.2005.08.010⟩. ⟨hal-02542170⟩

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