Electrical Properties and Electronic States of Molecular Conductors Based on Unsymmetrical Organometallic-Dithiolene Gold(III) Complexes

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• 作者：Kazuya Kubo ; Akiko Nakao ; Yasuyuki Ishii ; Takashi Yamamoto ; Masafumi Tamura ; Reizo Kato ; Kyuya Yakushi ; Gen-etsu Matsubayashi
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：June 16, 2008
• 年：2008
• 卷：47
• 期：12
• 页码：5495 - 5502
• 全文大小：719K
• 年卷期：v.47,no.12(June 16, 2008)
• ISSN：1520-510X

文摘

The electronic properties of cation radical salts derived from organometallic mixed-ligand complexes [(ppy)Au(S−S)] (ppy⁻ = C-dehydro-2-phenylpyridine(−); S−S²⁻ = dithiolene ligand) with Au(III)−C σ-bond were investigated. A 2:1 salt complex [(ppy)Au(C₈H₄S₈)]₂[PF₆] (C₈H₄S₈²⁻ = 2-{(4,5-ethylenedithio)-1,3-dithiole-2-ylidene}−1,3-dithiole-4,5-dithiolate(2−)) exhibited semiconductive behavior under ambient pressure (ρ_rt = 2.6 Ω cm, E_a = 0.03 eV). Magnetic measurements show that it is a Mott insulator close to the metal−insulator boundary. Raman and infrared spectra have revealed that the complex has a quasi-one-dimensional dimeric structure consisting of uniformly charged donor molecules. The complex exhibits metallic behavior at pressures above 0.8 GPa. In contrast, a similar compound [(ppy)Au(C₈H₄S₆O₂)]₂[BF₄] (C₈H₄S₆O₂²⁻ = 2-{(4,5-ethylenedioxy)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithiolate(2−)) is a band insulator.