The Solvent Regulatable Synthesis And Property Study Of Novel Polyoxovanadates

Polyoxovanadates are an important branch of polyoxometalates.Due to their unique structural diversity, they are widely used in electrochemistry, catalytic, photochemistry, biochemistry etc.This thesis is mainly divided into two parts:(1)To explore a green method of synthesis,and six polyoxovanadates of pyridinium or Imidazole ionic liquid based on the simple source of vanadium had been synthesizd by using ionic liquid and water as the reaction medium; (2) Three germanato-polyoxovanadates had been prepared under hydrothermal conditions by using GeO2 as the auxiliary,which are decorated with the different organic amine and transition metal.All the compounds had been characterized by FT-IR,X-ray diffraction,single-crystal,UV,XPS etc.The fluorescent and electrochemical properties of the compounds had also been investigated.1. Three novel Decavanadates had been prepared by using pyridinium ionic liquid and simple vanadium, firstly.(Bpy)6[V10O28]·11H2O (1)(Epy)4[H2V10O28]·12.5H2O (2)(Epy)4(DMSO)2[H2V10O28]·10H20 (3)In Compound 1 has a 1D Channel along the a axis by cation accumulation, and polyoxoanions are interspersed in the channels through the hydrogen bonding interaction.Interestingly, the polyoxoanions and water molecules in compound 2 are linked through O-H...O hydrogen bonds to form a spiral 1D chain structure,while cations are connected by the hydrogen bonds between the chain and chain. Polyoxoanions and cations in compound 3 are linked through hydrogen bonds and intermolecular force to form 3D supramolecular structure.The electrochemical properties of the three compounds had also been investigated.2. Three Imidazole ionic liquid-polyoxovanadates based on the simple source of NH4VO3 and NaVO3 had been prepared under conventional conditions by using ionic liquid and water as the reaction medium.(mIM)(Emim)5[V10O28]·9H2O (4)(Pmim)(Bmim)5[V10O28]·11H20 (5)(Emim)7(DMSO)2[H3V10O28] [H2V10O28]·4H2O (6)Cu(C12H8N2)Br2 (7)The polyoxoanions and cations in compound 4 are linked through hydrogen bonds or intermolecular force to form 3D supramolecular structure.The structure of compound 5 is similar to compound 4.In compound 6 two anions formed a dimer anion by O-H...O Bond, and the dimer anions formed a 1D porous structure along the b axis,meanwhile the dimer anions are lying between the channels by hydrogen bonding.3. Three germanato-polyoxovanadates had been prepared under hydrothermal conditions, which were decorated through the different organic amine and transition metal.H2[Zn(tren)]5[V15Ge6O48(H2O)]·4H2O (8){[Zn(en)2] [Zn2(en)(dien)(trien)] [Zn4(en)2(dien)2(trien)3]} [V15Ge6O48(H2O)]·7H2O (9)H2[Co(en)2] [Co(dien)]4[V15Ge6O48(H20)] (10)The discrete polyoxoanion cluster in compound 8 existed widely C-H...O and N-H...O hydrogen bonding,and the polyoxoanions formed a net framework by stacking. Compound 9 occurred in situ reaction of ethylenediamine,resulting in the generation of diethylenetriamine and ethylamine. In ab plane,polyoxoanion cluster [V15Ge6O48(H2O)]12- as a tetradentate ligand attached four germanato-polyoxovanadates anions around it by Zn2+ fragment to form a 2D layered structure staggered. The structure of compound 10 and 9 are similar. In be plane, polyoxoanion cluster [V15Ge6O4g(H2O)]12-,a tetradentate ligand,attached four germanato-polyoxovanadates anions around it by a bridging ligand [Co2(dien)2]4+ to form a 2D layered structure staggered.