Journal
DALTON TRANSACTIONS
Volume 40, Issue 9, Pages 1977-1983Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0dt01152e
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Funding
- NNS Foundation [21041006, 20971092]
- Soochow University
- Doctoral Foundation of Soochow University
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Though numerous metal-organic frameworks or polymers have been reported, the organic building blocks are usually not redox-active. On the other hand, some mono-, di- or tri-nuclear compounds with tetrathiafulvalene (TTF) have been prepared, although little is known about the coordination polymers combined with paramagnetic metals and organic TTF ligands. We report herein a series of coordination polymers of copper(II) and manganese(II) with TTF dicarboxylate ligand (L). Compound 1, [CuL(2,2-bpy)](n), is a one-dimensional (1-D) coordination polymer with five-coordinated square-pyramidal Cu(II) centers. Mn(II) complex 2, [MnL(2,2-bpy)](n), also takes a 1-D structure, showing a double-bridged mode by carboxylate groups. The 4,4-bipyridine compound 3, [MnL(4,4-bpy)(H2O)](n)center dot CH3CN, takes a 2-D grid network. A zinc(II) compound 4, [ZnL(4,4-bpy)(H2O)](n)center dot CH3CN, isomorphous structure with 3, is also presented. The electrochemical properties of the solid-state compounds were investigated by cyclic voltammetry using surface-modified electrodes. As usually observed in TTF derivatives, two sets of redox-waves were observed. The values of E-1/2(1) of compounds 1-4 are in the order of 2(Mn) approximate to 3(Mn) < 1(Cu) < 4(Zn), indicating that the metal coordination can affect the potential shift of the TTF ligand. Weak antiferromagnetic exchanges are observed for compounds 1, 2, and 3.
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