Molecular and Multidimensional Organic−Inorganic Hybrids Based on Polyoxometalates and Copper Coordination Polymer with Mixed 4,4‘-Bipyridine and 2,2‘-Bipyridine Ligands

Abstract

Three novel organic−inorganic hybrid materials with mixed 4,4‘-bipyridine and 2,2‘-bipyridine ligands, K[{CuI(2,2‘-bipy)}(4,4‘-bipy){CuI(2,2‘-bipy)}0.5]2[Mo8O26] (1), [CuI(4,4‘-bipy)]3[PMo10VIMo2VO40{CuII(2,2‘-bipy)}] (2), and [CuI(2,2‘-bipy)(4,4‘-bipy)0.5]2[CuI(4,4‘-bipy)]2[SiW12O40] (3) (2,2‘-bipy = 2,2‘-bipyridine, 4,4‘-bipy = 4,4‘-bipyridine), have been hydrothermally synthesized. Compound 1 is a novel β-[Mo8O26]4- polyoxoanion bisupported by copper(I) coordination cations with mixed 4,4‘-bipy and 2,2‘-bipy ligands. Compound 2 consists of the divalent copper {CuII(2,2‘-bipy)}2+ capped [PMo10VIMo2VO40]5- building blocks linked by {Cu(4,4‘-bipy)}nn+ linear cationic chains into a novel two-dimensional (2D) network. To the best of our knowledge, compound 2 exhibits an unprecedented 2D structure containing the divalent copper capped polyoxometalate as building blocks. The novel structure of 3 is composed of one-dimensional hybrid zigzag chains linked by {Cu(4,4‘-bipy)}nn+ chains into a three-dimensional (3D) framework via weak Cu−O interactions. The novelty of compound 3 is that it is the first time that a novel 3D framework has been formed by polyoxometalate and transition metal coordination polymer chains with mixed 4,4‘-bipy and 2,2‘-bipy.