A New Type of Three-Dimensional Hybrid Polymeric Haloplumbate Based on Rare High-Nuclear Heterometallic Clusters.

A series of new three-dimensional hybrid heterometallic haloplumbates [Pb8M(μ3-O)2X8(XH)(eg)3] n {H2eg = ethylene glycol; X = Cl, M = Co (1a), Ni (1b), Zn (1c); X = Br, M = Ni (2a), Zn (2b); X = I, M = Zn (3)} have been solvothermally synthesized and structurally characterized. Compounds 1a-c, 2a-b, and 3 consist of one-dimensional haloplumbate [Pb2X9] chains, and heptanuclear heterometallic [Pb6M(μ3-O)2(eg)3] clusters based on two [Pb3(μ3-O)(eg)1.5] cores share one M2+ ion, which are interconnected to generate three-dimensional heterometallic frameworks. Although a few heterometallic haloplumbates incorporating other metal complexes have been reported, they usually exhibit low-dimensional structures. The present heterometallic haloplumbates offer good examples of applying high-nuclear heterometallic [Pb6MO2(eg)3] clusters to construct a new type of high-dimensional hybrid heterometallic haloplumbate. Compounds 1a-b and 2a indicate unusual ferrimagnetic behavior. Their optical properties are investigated at room temperature, and density functional theory calculations of compounds 1c, 2b, and 3 are also studied.