Yun-Long Hou,* Yun-Lei Peng, Yingxue Diao, Jie Liu, Lizhuang Chen,* and Dan Li*
ABSTRACT: Crystalline coordination architectures with coordinatively unsaturated metal sites are of great importance for their attractive properties.Tunable side chains of the 4-formylimidazole here were employed for directing the subcomponent self-assembly of (CuIIN4)2(CuII)2 (1), {(CuIIN4)(CuII)2}n (2), and {L(CuII)2}n (3) under the same solvothermal conditions, giving the structural diversity. The unique square-planar CuII/NiIIN4 units with open metal sites can not only be in situ embedded in 1 and 2, but also be successfully immobilized in {(NiIIN4)2(CuI CN)9}n (4) and {(CuIIN4)2- (CuI CN)9}n (5), through the metalloligand strategy. Enzyme-like substratespecific activity was observed by employing 5 as a heterogeneous catalyst, which exhibits increased activity and high selectivity toward the catalytic oxidation of 1-phenylethyl alcohol derivatives. This work presents two promising methodologies for the introduction of controllable open metal sites in versatile crystalline coordination complexes and their application in the substrate-selective catalytic oxidation reaction.
