An organic-inorganic hybrid semiconductor material based on Lindqvist polyoxomolybdate and a tetra-nuclear copper complex containing two different ligands

摘要

A 3D organic-inorganic hybrid compound based on the Lindqvist-type polyoxometalate, [{Cu(phen)}_3-{Cu(μ_2-ox)_3}{Mo_6O_(19)}] (1) (phen = 1,10-phenanthroline, ox = oxalate), has been synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR, TG, PXRD, XPS, UV-vis, and single-crystal X-ray diffraction. In compound 1, three C_2O_4~(2-) ligands bridge one Cu atom and three Cu(phen) fragments to form a tetra-nuclear copper(II) coordination complex [{Cu(phen)}_3{Cu(μ_2-ox)_3}]~(2+) unit. The six-node [Mo_6O_(19)]~(2-) clusters are interweaved by the 6-connected tetranuclear copper(II) complex units into an intricate 3D network structure, exhibiting a 4~(12)?6~3-nbo (sodium chloride-type) topology. Compound 1 exhibits the highest connectivity of Lindqvist-type POM hybrid materials. The electrochemical behavior of 1-CPE has been investigated in detail. Furthermore, a diffuse reflectivity spectrum of 1 reveals the presence of an optical band gap and the nature of semiconductivity with a large energy gap. A magnetic susceptibility study reveals predominant antiferromagnetic interactions between the Cu~(II) bridge units.