Synth Eses, Crystal Structures And Properties Of Rare-earth-substitutcd Polyoxotungstate Derivatives

The paper can be divided into two parts. In the first part, on the basis of molecular design andassembly, adopting rare-earth （RE） or RE and multicarboxylic ligands, fourteen novel RE-substitutedphosphotungstate derivatives have been successfully synthesized by conventional aqueous method andfurther charactered by single-crystal X-ray diffraction, spectroscopic properties （IR, XRPD）,thermogravimetric analyses, photoluminescence and magnetic properties.I. Two types of novel oxalate-bridging RE-substituted Keggin-type phosphotungstates have beensuccessfully prepared by reaction of the monovacant Keggin-type [α-PW₁₁O₃₉]7with RE and oxalateligands in aqueous solution.II. Three novel triangular and six dimeric RE-substituted Dawson-type phosphotungstates havebeen successfully obtained by reaction of the saturated precursor [α-P2W18O62]6with RE cations.In the second part, on the basis of molecular design and assembly, adopting RE-TM and organicligands, sixteen novel RE-TM polyoxometalate derivatives have been successfully synthesized underhydrothermal methods and further charactered by single-crystal X-ray diffraction, spectroscopic properties（IR, XRPD）, thermogravimetric analyses, photoluminescence property and photocatalysis properties.I. Eight novel organic-inorganic hybrid lacunary Keggin silicotungstate RE-TM heterometallicderivatives have been successfully isolated under hydrothermal conditions.II. The hydrothermal reactions of Keggin-type silicotungstates with RE-TM heterometals in thepresence of mixed ligands pyrazine-2,3-dicarboxylate and ethylenediamine generate seven novelorganic-inorganic hybrid supramolecular assemblages.II. The hydrothermal reactions of Keggin-type silicotungstates with RE-TM heterometals in thepresence of mixed ligands oxalate and ethylenediamine produce one novel2D organic-inorganic hybridsilicotungstate assemblage.