Syntheses, Crystal Structures And Properties Of Rare-earth And Alkaline-earth Metals Derivatives Based On Monovacant Keggin Phosphotungstate

On the basis of molecular design and assembly, a series of novel organic-inorganic dimeric structures and 1D chain structures based on the monolacunary polyanion [α-PW11O39]7? and rare earth/alkaline-earth /transition metals have been synthesized by the conventional aqueous methods and characterized by X-ray crystallography, spectroscopic, thermal, electrochemical, luminescent and magnetic properties.(1) Two kinds of unprecedented polyoxometalate rare-earth metal derivatives (2:2 type) and a novel 1D zigzag chain rare-earth metal derivative (1:1 type), containing lacunary Keggin-type heteropolyanion have been successfully synthesized and characterized by X-ray crystallography. In these compounds, three kinds of clusters with the Ln3+/ [α-PW11O39]7- ratio of 1:1 was observed. The two kinds of moiety (2:2 type) show the novel cluster based on the rare-earth and monolacunary Keggin polyoxometalate. The luminescent properties, magnetic properties, electrocatalytic properties and thermal properties of the series of dimers were investigated.(2) We have successfully synthesized two novel alkaline-earth metal substituted phosphotungstate derivatives based on the lacunary Keggin-type heteropolyanion and alkaline-earth metal cations displaying a one dimensional arrangement which is the first crystal structure that introduced the alkaline-earth metal cations (Ca2+ and Sr2+) into the [α-PW11O39]7- polyanion system.(3) A novel polyoxometalate, [C16H36N][Cu(2,2-bipy)3][PW12O40]?CH3CN?H2O, based on a Keggin-type heteropolyanion [PW12O40]3- and transition metal coordination cations. The compound was characterized by IR and X-ray single-crystal diffraction.(4) A novel organic-inorganic polymer has been synthesized by hydrothermal reaction, and characterized by IR, TG-DTA and single-crystal X-ray diffraction. It respresents the transition metal substituted phosphotungstate organic-inorganic derivatives based on the lacunary Keggin-type heteropolyanion and transition metal coordination cations.