Phosphomolybdate cluster based solids mediated by transition metal complexes

Reaction of molybdate and phosphate precursors in the presence of 3d transition metal ions and pyrazole (pz) under hydrothermal condition resulted in the crystallization of four new phosphomolybdate cluster based solids: (pz)2[{Co(pz)4}5{P2Mo5O23}2]·6H2O (1), (pz){Ni(pz)4(H2O)2}[{Ni(pz)4}5{P2Mo5O23}2]·2H2O (2), {Cu(pz)4(H2O)2}[{Cu(pz)4}{Cu(pz)4(H2O)}{P2Mo5O23}]·2H2O (3) and (pz)[{Zn(pz)3}3{P2Mo5O23}]·2H2O (4). In all the solids, a metal complex {M(pz)n} covalently links{P2Mo5O23} clusters to form a chain. The dimensionality of the structures differs in the way the chains link or self assemble with counter ions and water molecules. To the best of our knowledge, 4 is the first example of a zinc complex incorporated with {P2Mo5O23} cluster. The paper discusses the self assembly occurring between in situ metal pyrazole complex and phosphomolybdate clusters through coordinate/covalent and noncovalent interactions during crystallization of a particular solid.