Abstract

Solvothermal reaction of CuCl2·2H2O and 2-(4-pyridyl)benzimidazole (PyHBIm) in a acetonitrile-water mixed solvent afforded a mixture of [CuI2CuII(CN)2(PyHBIm)2Cl2]n (1) and [CuII(PyH2BIm)2Cl4] (2). Complex 1 is a mixed-valence 1D ribbon Cu(I,II)-cyanide coordination polymer. One Cu(II) center linearly links two Cu(I) ions via two μ2-CN bridges. XPS spectrum and bond valence sum (BVS) analysis have confirmed the mixed-valence characteristics. Cu(II) ion adopts a centrosymmetric square-planar geometry surrounded by two cyanides and two pyridyl groups. Cu(I) ions adopt a trigonal geometry coordinated by cyanide, imidazole group and Cl− anion. The cyanide ligand is in situ generated from the cleavage of acetonitrile solvent, which indicates that acetonitrile is an environmentally friend cyanating agent. The mechanism of acetonitrile in situ cleavage under solvothermal condition is explained. Complex 2 is a centrosymmetric mononuclear Cu(II) compound. Four equivalent Cl− anions lie on the equatorial plane. The protonated PyH2BIm+ cation as a monodentate ligand coordinates to Cu(II) center via pyridyl terminal.

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