Two New Supramolecular Hybrids Based on Bi-capped Keggin {PMo12V2O42} Clusters and Transition Metal Mixed-organic-ligand Complexes

Two supramolecular compounds [Cu（imz）2][Cu（phen）（imz）]2{[Cu（phen）]2[PMo6^VIMo6^VV2^IVO42]}（1） and [Co2（2,2＇-bpy）4（C2O4）][Co（2,2＇-bpy）3][PMo7^VIMo5^VV2^IVO42]（2,2＇-bpy）0.5.H2O（2）（phen=1,10＇-phenanthroline, imz= imidazole, 2,2＇-bpy=2.2＇-bipyridine） have been synthesized hydrothermally and characterized by elemental analyses, infrared spectrum, UV-Vis, X-ray photoelectron spectroscopy（XPS）, electron spin resonance（ESR） spectra, thermogravimetry analyses and single crystal X-ray diffraction analyses. Single-crystal X-ray diffraction analyses revealed that both the compounds represent the examples of compounds based on the bi-capped Keggin polyoxoanion {PMo12V2O42} and transition metal mixed-organic-ligand coordination complexes. Compound 1 consists of bi-capped Keggin polyoxoanion [PMo12V2O42]5 supported copper coordination groups, which are further interconnected with two types of copper complex fragments forming a 3D supramolecular framework via π-π stacking, C-H…O and N-H…-O hydrothermal bonding interactions. Compound 2 is a new hybrid consisted of polyoxoanion [PMo12V2O42]^4-, [Co2（2,2＇-bpy）4（C2O4）]^2＋ and [Co（2,2＇-bpy）3]^2＋. There are no direct interactions in compound 2, but the polyoxoanions together with two different cobalt complex groups construct a 3D supramolecular network through C-H…O hydrogen bonding interactions.