Phosphomolybdate clusters as molecular building blocks in the design of one-, two- and three-dimensional organic–inorganic hybrid materials

An attractive approach to the design of inorganic solids exploits the tethering of inorganic clusters through organic spacers to produce hybrid materials with composite properties. We have recently described a modified strategy in which polyoxometalate clusters are linked through organic subunits to give an anionic hybrid substructure which may be further modified through the introduction of secondary metal–ligand complex (SMLC) cations, serving as a third component building block. In this application, the molybdophosphonate cluster {Mo 5O 15(O 3PR) 2} 4− serves as a secondary building unit (SBU) with alkyl (CH 2) n or aromatic –(C 6H 4) n – tethers providing one-dimensional structural expansion. A binucleating ligand such as tetrapyridylpyrazine (tpyprz) is used to bridge secondary metal sites into a binuclear {Cu 2(tpyprz)} 4+ SBU which may link phosphomolybdate clusters into two- or three-dimensional structures. The influence of a variety of structural determinants is discussed, including the tether length of the diphosphonate ligand, the coordination preferences of the secondary metal, expansion of the ligand component of the SMLC, and substitution of As for P in the oxide SBU. A building block approach to the design of new materials exploits the linkage of polyoxometalate clusters through organic subunits to give an anionic hybrid substructure which may be further modified through the introduction of secondary metal–ligand complex (SMLC) cations, serving as a third component. The representative example, [{Co 3(tpyprz) 2(H 2O) 3}[Mo 5O 15{O 3P(CH 2) 3PO 3}] 2], is illustrated, highlighting the non-framework domain occupied by solvate molecules.