Syntheses,Structures And Properties Of Polyoxomolybdates Or Polyoxotungstates Constructed By Organophosphonates

Functionalized POMs with organophosphonate have become an important and hotresearch topic in the POMs family due to its novel structure and excellent performance.Organophosphonates are an important kind of organic ligands with the potential applications in materials,medicine and catalysis,owing to their various structures,wide varieties as well as very rich coordination modes.In this Master Degree Thesis,a series of lanthanide（Ln）-containing organophosphonate-based polyoxomolybdates and four member of transition-metal（TM）incorporate into organophosphonate-functionalized polyoxomolybdates or polyoxotungstates have successfully prepared by one-pot.The given compounds are characterized by single-crystal X-ray diffraction,elemental analyses,X-ray diffraction,spectroscopic properties（IR,UV）,thermogravimetric analyses and X-ray photoelectron spectroscopy,and magnetic properties,photoluminescence properties and catalytic for oxidation of thioethers.The contents of this dissertation displays following:I A series of Ln-containing phosphonoacetic acid-based polyoxomolybdatesK₄H₅[Ln₃（H₂O）₁₄{(Mo₈O₂₄)（O₃PCCOO）₃}₂]·23H₂O[Ln=Gd（1）,Tb（2）,Dy（3）]have successfully prepared by the reaction of sodium molybdate and phosphonoacetic acid with Ln ions.Compounds 1–3 contain the same structure of the polyoxoanions.The catalysis properties of 1–3 for thioether oxidization have been investigated using hydrogen peroxide（H₂O₂）as an oxidant.The catalysis study demonstrated that 2 shows good catalytic activity toward the reaction of alkyl,aryl alkyl thioethers and sulfur-containing compounds benzothiophene（BT）,dibenzothiophene（DBT）,and4,6-dimethyldibenzothiophene（4,6-DMDBT）oxidating into sulfones.K₄H₅[Gd₃（H₂O）₁₄{(Mo₈O₂₄)（O₃PCCOO）₃}₂]·23H₂O（1）K₄H₅[Tb₃（H₂O）₁₄{(Mo₈O₂₄)（O₃PCCOO）₃}₂]·23H₂O（2）K₄H₅[Dy₃（H₂O）₁₄{(Mo₈O₂₄)（O₃PCCOO）₃}₂]·23H₂O（3）II Two novel TM-containing ATMP-functionalized polyoxomolybdates have beensuccessfully obtained by a one-pot reaction of（NH₄）₆Mo₇O₂₄·4H₂O,TM and ATMP.The polyanions of compounds 4 and 5 can be described as six[TeMo₆O₂₁{N（CH₂PO₃）₃}]^5-units linked by six Cu/Co atoms,creating a cage with a small cavity.Compound 4 and 5,containingIII a 36-molybdenum-membered cluster,represent the highest nuclearity of metal atoms in organophosphonate-based POMs chemistry.（NH4）₉Na₄H₁₇[Co（H₂O）TeMo₆O₂₁{N（CH₂PO₃）₃}]₆·20H₂O（4）（NH₄）₁₆Na₇H₇[Cu（H₂O）TeMo₆O₂₁{N（CH₂PO₃）₃}]₆·12H₂O（5）IV A new TM-subtituted glyphosate-functionalized polyoxomolybdates and two member of a new family of TM-containing glyphosate-functionalized Polyoxotungstates have been successfully prepared in aqueous solution by a one-pot reaction.Magnetic studies reveal that 6–8 exhibit the antiferromagnetic couplingin the cluster.Cs₂Na₉[H{Co（H₂O）₄}(TeMo₆O₂₁)₂{Co（OOCCH₂NCH₂PO₃）₂}₃]·34H₂O（6）Na₈H₄[{Co（H₂O）₄}(SeW₆O₂₁)₂{Co（OOCCH₂NCH₂PO₃）₂}₃]·24H₂O（7）Cs₂Na₂H₈[{Co（H₂O）₄}(SeW₆O₂₁)₂{Co（OOCCH₂NCH₂PO₃）₂}₃]·29H₂O（8）...