Two new supramolecular hybrids based on bi-capped Keggin {PMo₁₂V₂O₄₂} clusters and transition metal mixed-organic-ligand complexes

Abstract

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 inter-connected 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.

Keywords

Transition metal mixed-organic-ligand complex / Keggin polyoxometalate / Hydrogen bond / π⋯π Stacking interaction

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