Study On Synthesis, Structures And Spectra Of Sb(Bi) Contained Oxygen-clusters

Because of particular catalyst properties, anti-virus activity and photoelectric,magnetic properties, metal-oxygen clusters have been researched for a long time. Synthesis of novel structure of metal-oxygen clusters has aroused a lot of interests of chemical researchers. After the consultant of the literature, we put the emphasis on the Sb and Bi contained metal-oxygen clusters. We synthesized ten kinds of crystals of Sb and Bi contained metal-oxygen clusters in water and hydrothermal conditions, and determined their structures. They can be divided into two groups:(1) Molybdoantimonates which have open- frameworks:NaSbMoO5 (Ⅰ)KSbMoO5 (Ⅱ)Na4Sb12Mo5O35 (Ⅲ)(2) Sb and Bi contained polyoxometalate Na5.7H1.3SbMo3V3O21Cl3.2.7H2O (Ⅳ)K3HSbV3Mo3O21.9H2O (Ⅴ)K1.5H3Sb1.5MoO9·2H2O (Ⅵ) (NH4)2H2.5Sb1.5MoO9·H2O (Ⅶ)Na2H1.5Sb0.5W5.5O19.1.5H2O (Ⅷ)Co2.5[BiCoW10O35(H2O)3].27H2O (Ⅸ)Na3H2[Ce3(H2O)18Bi2W22O76].23H2O (Ⅹ)compound (Ⅰ),(Ⅱ)and(Ⅲ) are molybdoantimonates which have the structures of 2D or 3D framework. Compound (Ⅳ)and (Ⅴ)are SbⅤ containing molybdovanadates and to our knowledge there isn't any homogeneous have been reported. Different from compound (Ⅰ),(Ⅱ)and(Ⅲ), compound(Ⅵ)and(Ⅶ) are the molybdoantimonates in which the valence of Sb is 5+ . And the structures of them contain Sb6Mo4O36 clusters. The structure of compound(Ⅷ),(Ⅸ)and(Ⅹ)have the XW9 units (X= SbⅢ (compound Ⅷ )；X＝BiⅢ(compound Ⅸ andⅩ)) which are derived from Keggin structures And we also employed IR, Raman, DRS, fluorescent spectra, TGA and X-ray power diffraction to characterize some compounds. In IR and Raman spectra, we ascribed the characteristic peaks of polyoxometalates to corresponding vibration frequencies. In UV-Vis DRIS spectra, the LMCT bands of Ot→M are found at about 205nm and the LMCT bands of Ot→M split into two peaks. The fluorescent spectra of some solid compounds were obtained by the excited wavelength is 220nm or above 300nm. At last, quantum chemistry calculations were carried out on four kinds of metal-oxygen clusters.