Tetrathiafulvalene−Tetracarboxylate: An Intriguing Building Block with Versatility in Coordination Structures and Redox Properties

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• 作者：Yu-Rong Qin ; Qin-Yu Zhu ; Li-Bin Huo ; Zheng Shi ; Guo-Qing Bian ; Jie Dai
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：August 16, 2010
• 年：2010
• 卷：49
• 期：16
• 页码：7372-7381
• 全文大小：1138K
• 年卷期：v.49,no.16(August 16, 2010)
• ISSN：1520-510X

文摘

The synthesis of the transition metal coordination polymers containing a tetrathiafulvalene (TTF) moiety substituted with a tetracarboxylate group of the formulas [Mn(L)_0.5(phen)(H₂O)₂]_n·nH₂O (1), [Mn(L)_0.5(bpy)]_n·nH₂O (2), [Mn(L)_0.5(bpy)(CH₃OH)]_n·2nH₂O (3), and [Cu(L)_0.5(bpy)(DMF)]_n·n(DMF) (4) (L⁴⁻ = TTF-tetracarboxylate; phen = 1,10-phenanthroline; bpy = 2,2′-bipyridine) is reported. Complex 1 is a two-dimensional (2-D) coordination polymer constructed of infinite carboxylate bridged Mn(II) chains and TTF moiety linkages. Complex 2 possesses a 3-D polymeric structure formed by infinite −Mn−(O−C−O)₂−Mn− bridged one-dimensional (1-D) chains, which are further coordinated by TTF-tetracarboxylate ligands of two different orientations. Both complexes 3 and 4 show 1-D extended chain structures but are constituted by different dinuclear metal(II) units with a −Mn−(O−C−O)₂−Mn− bridge in 3 and a −Cu−(O)₂−Cu− bridge in 4. Electrochemical study of the solid-state compounds attests to the redox activity of the coordination system. Magnetic investigations reveal the existence of antiferromagnetic interactions between magnetic centers in complexes 3 and 4, while in 1, the paramagnetic metallic centers are isolated, in agreement with the solid-state structure.