New BDH-TTP/[MIII(C5O5)3]3鈥?/sup> (M = Fe, Ga) Isostructural Molecular Metals

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• 作者：Luca Pilia ; Elisa Sessini ; Flavia Artizzu ; Masahiro Yamashita ; Angela Serpe ; Kazuya Kubo ; Hiroshi Ito ; Hisaaki Tanaka ; Shin-ichi Kuroda ; Jun-ichi Yamada ; Paola Deplano ; Carlos J. G贸mez-Garc铆a ; Maria Laura Mercuri
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：January 7, 2013
• 年：2013
• 卷：52
• 期：1
• 页码：423-430
• 全文大小：493K
• 年卷期：v.52,no.1(January 7, 2013)
• ISSN：1520-510X

文摘

Two new isostructural molecular metals鈥?BDH-TTP)₆[M^III(C₅O₅)₃]路CH₂Cl₂ (BDH-TTP = 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene, where M = Fe (1) and Ga (2))鈥攈ave been prepared and fully characterized. Compound 1 is a molecular conductor showing paramagnetic behavior, which is due to the presence of isolated [Fe(C₅O₅)₃]^{3鈥?/sup> complexes with high-spin S = 5/₂ Fe(III) metal ions. The conductivity originates from the BDH-TTP organic donors arranged in a 魏-type molecular packing. At 4 kbar, compound 1 behaves as a metal down to 100 K, showing high conductivity (10 S cm鈥?) at room temperature. When applying a pressure higher than 7 kbar, the metal鈥搃nsulator (M-I) transition is suppressed and the compound retains the metallic state down to low temperatures (2 K). For 1, ESR signals have been interpreted as being caused by the fine structure splitting of the high-spin (S = 5/₂) state of Fe(III) in the distorted octahedral crystal field from the ligands. At 4 kbar, the isostructural compound 2 behaves as a metal down to 100 K, although it is noteworthy that the M-I transition is not suppressed, even at pressures of 15 kbar. For 2, only the signal assigned to delocalized 蟺-electrons has been observed in the ESR measurements.}