Syntheses, Structures And Properties Of Polyoxomolybdates Constructed By Organophosphonate

Polyoxometalates constructed by organophosphonate have attracted wide attention not only because oftheir structural diversity but also due to their potential applications in the fields of sorption, catalysis,medicine and functional materials. At present, the most research are focused on the system containingtransition metals, however, the lanthanide-containing analogues are not reported. We have dedicatedourselves to studying this research topic since2010, finally, a series of lanthanide-containingorganodiphosphonate-functionalized polyoxomolybdate were first reported by us. Moreover, two novelorganophosphonate derivatives of polyoxomolybdates have been prepared in this context. The obtainedcompounds were characterized by single-crystal X-ray diffraction, spectroscopy properties, fluorescence,thermogravimetric and drug activity analysis.1. Seven novel lanthanide-containing organobisphosphonate-functionalized polyoxomolybdate cages（HDMA）₂（TBA）[Ce₅（DMF）13（H₂O）11{（Mo₃O₈）（O₃PCOCH₃PO₃）}₆]·4DMF·6H₂O （1）（HDMA=dimethylammonium）,（TBA）₃[Ln₅（DMF）11（H₂O）14{（Mo₃O₈）（O₃PCOCH₃PO₃）}₆]·DMF·5H₂O [Ln=Pr^Ⅲ（2）, Nd^Ⅲ（3）, Sm^Ⅲ（4）] and （HDMA）3{[Ln5（DMF）12（H₂O）12{（Mo₃O₈）（O₃PCOCH₃PO₃）}₆]·6DMF·nH₂O[Ln=Eu^Ⅲ（5）, n=0; Gd^Ⅲ（6）, n=2; Tb^Ⅲ（7）, n=2] were first prepared from （TBA）4[Mo8O26]（TBA=（n-C4H9）4N）,1-hydroxyethylidenediphosphonate （H₂O3PCCH3OHPO3H₂=HEDP） and different lanthanidesalts. The structures of1–7comprise two unprecedented windmill-type {Ln（DMF）m（H₂O）n{（Mo₃O₈）（O₃PCOCH₃PO₃）}₃}₆（m=1,2,3, n=0,1,2） linked by three Ln^Ⅲbridges, thus forming cagestructures.2. A new organodiphosphonate-functionalized polyoxomolybdate （TBA）₃[（O₃PCOHCH₃PO₃）Mo₆O₁₈H（DMF）]·4.5H₂O （8） has been synthesized by the reaction of （TBA）₄[Mo₈O₂6] and HEDP. Crystal structureanalysis reveals that8represents another novel {P2Mo6} unit in the chemisty of phosphomolybdates.3. An organodiphosphonate-functionalized polyoxomolybdate [（n-C₄H₉）₄N]₂[（NH₂CH₂PO3）2Mo5O15]·[CH₃NHCH₃]₂·H₂O has been synthesized by the reaction of （TBA）4[Mo8O26] and diethylenetriaminepenta（methylene phosphonic acid）（DTPMP）, the obtained compound exhibits Strandberg type structure.