Syntheses, Crystal Structures And Properties Of Polyoxomolybdates Constructed By Organophosphonate Ligands

Organophosphonates have a wide varity and applications in the fields of medicine, catalysis andfunctional materials. As a result, it has been a hot topic of inorganic chemistry, organic chemistry andbiological chemistry. In addition, the surface oxygen atoms of polyoxometalates （POMs）, have strongcoordination ability and thus POMs have become important inorganic building block with novel structuresand benign properties. Organophosphonate incorporated into POMs which have attracted wide attention notonly due to their novel structures, but the potential properties of the obtained compounds. In this paper, wehave dedicated ourselves to synthesize novel organophosphonate-based POMs and obtained severalexamples according to this design. The given compounds were characterized by X-ray single-crystaldiffraction, infrared spectroscopy, thermogravimetric, XRD, fluorescence, optical studies, drug activity andmagnetism analysis.1. Three novel polyoxomolybdates constructed by ATMP ligandsNa₅H₇[{N（CH₂PO₃）₃}Mo₆O₁₆（OH）（H₂O）₄]4·18H₂O （1） Na₂H₄{（CH₃COO）[N（CH₂PO₃）₃]-Mo₆O17（OH）}·13H₂O （2） and Na₂（NH₄）₄[Mn2Na₂（H₂O）₂]{[HN（CH₂PO₃）₂]（CH₃COO）PMo₆O₂₂}2·16H₂O （3）have been first prepared in aqueous solution. Polyanion1can be regarded as assembly of four[{N（CH₂PO₃）₃}Mo₆O17（OH）（H₂O）₃]3subunits with crown shape. Compounds2and3are two examples ofhexanuclear Mo（VI） clusters which extended into two-dementional structures.2. Two new organodiphosphonate-functionalized polyoxomolybdatesNa4H₂[（Mo₃O₈）₂（O）{O₃PC（O）（CH₂-3-C₅NH₅）PO₃}2]·12H₂O （4） Na8[（Mo₃O₈）{O₃PC（O）（CH₂-3-C₅NH₅）PO₃}]4·30H₂O （5） have been synthesized by the reaction of1-hydroxo-2-（3-pyridyl）ethylidenebisphosphonate. Two polyanions are composed of the same building blocks and can be describedas dimeric and tetrameric assembly of [（Mo₃O₈）{O₃PC（O）（CH₂-3-C₅NH₅）PO₃}]2–subunits, respectively.3. Two HEDP-based polyoxomolybdates Na₂H₄[Mo₃O₈{H₂O₃PC（CH₃）（OH）PO₃}{HO₃PC（CH₃）（OH）PO₃}]2·36H₂O （6） Na（NH₄）7{Cr[Mo2O6{O₃PC（CH₃）（OH）PO₃}]2-[H₆CrMo₆O24]}·11H₂O （7） have been successfully isolated by the conventional aqueous methods.Compound6shows a1-D chains structure and compound7exbihits an infinitely extended2-D network.