open access

https://hdl.handle.net/2115/52228

Structural Characteristics in a Stable Metallic ET Salt with Unusually High Oxidation State (ET: Bis(ethylenedithio)tetrathiafulvalene)

英語

2012-03

Chemical Society of Japan

Bulletin of the Chemical Society of Japan

85(3)

335-340

Electrolysis of ET in a mixed solvent of methanol/CHCl3 with bromide yielded (ET)3(Br3)5, in which an unusually high formal charge of ET^[5/3+] is achieved. ET forms a two-dimensional conducting sheet incorporating Br3-[-]. Despite the high formal charge of the ET cations, the strong electrostatic attractions between the ET cations and Br3^[-] support aggregation of the ET cations, allowing sufficient π-π overlap for delocalization of the π-electrons. The crystal shows stable metallic behavior down to low temperatures, being consistent with the metallic band structure with two-dimensional Fermi surfaces and Pauli-like paramagnetism down to low temperatures. The lack of any indication of instability in the metallic phase due to correlation effects is considered to result from an ionic-crystal-like structure, in which the lattice is more resistant toward lattice deformation and/or shrinkage than in typical partially oxidized salts with low formal charges.

学術雑誌論文

Accepted Manuscript

0009-2673