Solvothermal Subcomponent Self-Assembly of Cubic Metal-Imidazolate Cages and Their Coordination Polymers

A series of Ni-imidazolate cubic cages, one-dimensional and two-dimensional coordination polymers based on the cubic cages, have been prepared by solvothermal subcomponent self-assembly of 5-methyl-4-formylimidazole, m-xylylenediamine, and Ni-II salts with varied anions. These compounds have been characterized by single-crystal X-ray diffractions, elemental analysis, IR spectra, and powder X-ray diffractions. The formation of an oligomerized coordination cage or an infinite coordination polymer depends on the anions chosen. An oligomerized 8-nuclear Ni-imidazolate cubic cage is formed when the anion Cl-, Br-, I-, SCN-, NO2-, or NO3- is utilized in the reactions, and a two-dimensional coordination polymer based on the Ni-inlidazolate cubic cage will be obtained when N-3(-), (CN)(2)N-, or (CN)(3)C- act as the anions. When only ClO4- or both ClO4- and [Ni(C4N2S2)(2)](2-) (C4N2S2 = dimercaptomaleonitrile) as anions exist in the reaction mixture, a ladder-like one-dimensional coordination polymer based on the Ni-imidazolate cubic cage and formate is formed unpredictably.