Department of Chemistry and Key Laboratory of Organic Synthesis of Jiangsu Province, Soochow University, Suzhou, 215123, People's Republic of China.
Dalton Trans. 2011 Mar 7;40(9):1977-83. doi: 10.1039/c0dt01152e. Epub 2011 Jan 31.
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), is a one-dimensional (1-D) coordination polymer with five-coordinated square-pyramidal Cu(II) centers. Mn(II) complex 2, MnL(2,2-bpy), also takes a 1-D structure, showing a double-bridged mode by carboxylate groups. The 4,4-bipyridine compound 3, MnL(4,4-bpy)(H(2)O)·CH(3)CN, takes a 2-D grid network. A zinc(II) compound 4, ZnL(4,4-bpy)(H(2)O)·CH(3)CN, 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) ≈ 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.
虽然已经报道了许多金属有机骨架或聚合物，但有机构筑块通常不是氧化还原活性的。另一方面，已经制备了一些具有四硫富瓦烯（TTF）的单核、二核或三核化合物，尽管对于与顺磁金属和有机 TTF 配体结合的配位聚合物知之甚少。我们在此报告了一系列铜（II）和锰（II）与 TTF 二羧酸配体（L）的配位聚合物。化合物 1，CuL(2,2-bpy)，是一种一维（1-D）配位聚合物，具有五配位的平面四方 Cu(II)中心。Mn(II)配合物 2，MnL(2,2-bpy)，也采用 1-D 结构，通过羧酸根显示双桥接模式。4,4-联吡啶化合物 3，MnL(4,4-bpy)(H(2)O)·CH(3)CN，采用二维网格网络。呈现出与 3 相同的结构的锌（II）化合物 4，ZnL(4,4-bpy)(H(2)O)·CH(3)CN，也被提出。通过使用表面修饰电极的循环伏安法研究了固态化合物的电化学性质。如通常在 TTF 衍生物中观察到的那样，观察到两组氧化还原波。化合物 1-4 的 E(1/2)(1)值的顺序为 2(Mn)≈3(Mn)<1(Cu)<4(Zn)，表明金属配位可以影响 TTF 配体的电位移动。对于化合物 1、2 和 3，观察到弱的反铁磁交换。
