Dinuclear Ruthenium Complex Based on a π-Extended Bridging Ligand with Redox-Active Tetrathiafulvalene and 1,10-Phenanthroline Units

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• 作者：Bin Chen ; Zhong-Peng Lv ; Carol Hua ; Chanel F. Leong ; Floriana Tuna ; Deanna M. D’Alessandro ; David Collison ; Jing-Lin Zuo
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：May 2, 2016
• 年：2016
• 卷：55
• 期：9
• 页码：4606-4615
• 全文大小：552K
• 年卷期：0
• ISSN：1520-510X

文摘

The synthesis of a π-extended bridging ligand with both redox-active tetrathiafulvalene (TTF) and 1,10-phenanthroline (phen) units, namely, bis(1,10-phenanthro[5,6-b])tetrathiafulvalene (BPTTF), was realized via a self-coupling reaction. Using this ligand and Ru(tbbpy)₂Cl₂ (tbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine), the dinuclear ruthenium(II) compound [{Ru(tbbpy)₂}₂(BPTTF)](PF₆)₄ (1) has been obtained by microwave-assisted synthesis. Structural characterization of 1 revealed a crossed arrangement of the TTF moieties on adjacent dimers within the crystal structure. The optical and redox properties of 1 were investigated using electrochemical, spectroelectrochemical, electron paramagnetic resonance (EPR), and absorption spectroscopic studies combined with theoretical calculations. One exhibits a rich electrochemical behavior owing to the multiple redox-active centers. Interestingly, both the ligand BPTTF and the ruthenium compound 1 are EPR-active in the solid state owing to intramolecular charge-transfer processes. The results demonstrate that the TTF-annulated bis(phen) ligand is a promising bridging ligand to construct oligomeric or polymeric metal complexes with multiple redox-active centers.