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)

• Published in: Synthetic metals Vol. 155; no. 3; pp. 527 - 538
• Main Authors: Zorina, L.V., Khasanov, S.S., Simonov, S.V., Shibaeva, R.P., Kushch, L.A., Buravov, L.I., Yagubskii, E.B., Baudron, S., Mézière, C., Batail, P., Canadell, E., Auban-Senzier, P.
• Format: Journal Article
• Language: English
• Published: Lausanne Elsevier B.V 01.12.2005; Amsterdam Elsevier Science; New York, NY Elsevier
• Subjects: Band structure; Chemical Sciences; Cristallography; Low-dimensional organic conductors; Material chemistry; X-ray diffraction; Low-dimensional organic conductors; X-ray diffraction; Band structure
• ISSN: 0379-6779; 1879-3290
• DOI: 10.1016/j.synthmet.2005.08.010

Four new radical cation salts based on the amide functionalized EDT-TTF organic donors EDT-TTF-CONH 2 (D1) and EDT-TTF-(CONH 2) 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: σ RT( 2)/ σ RT( 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).