Solid state coordination chemistry of molybdenum oxides: Construction of bimetallic organic–inorganic hybrid materials from Keggin clusters and copper-imine building blocks

The unexpected hydrolysis of organophosphonic acid ligands under hydrothermal reaction conditions yielded four bimetallic oxide materials incorporating Keggin type polyanions. The one-dimensional [Cu4O(Htpyprz)(tpyprz)2Cl4] [Mo12PO40] (1), [Cu6(4-pyrtet)2(4-Hpyrtet)4][MoVMoV11IPO40]·2.5H2O (2·2.5H2O), and [Cu3(OH)(4-pyrtet)2(4-Hpyrtet)2(H2O)2] [Mo12PO40]·10.5H2O (3·10.5H2O) and the two-dimensional [Cu3(OH)(4-pyrtet)3(4-H2pyrtet)(H2O)] [Mo12PO40]·7.5H2O (4·7.5H2O) (tpyprz = tetra-4-pyridyl pyrazine; 4-Hpyrtet = 4-pyridyltetrazole) demonstrate the variety of ways in which Keggin clusters may influence the configuration of the secondary metal–ligand substructure.

Graphical abstractHydrothermal reactions of an appropriate molybdenum oxide, an organodiphosphonic acid, cupric acetate and an organonitrogen ligand provided a series of bimetallic oxides incorporating the {Mo12PO40}n− Keggin cluster as a building block. As shown in the pictogram, a variety of one- and two-dimensional copper/organonitrogen substructures are observed.Figure optionsDownload full-size imageDownload as PowerPoint slide