Hydrothermal Synthesis And Characterization Of Novel V/P/O Inorganic-organic Hybrid Compound

The design and synthesis of inorganic-organic hybrid materials have generated significant interest for their potential applications in fields of catalysis, adsorption, separation, host-guest chemistry, biology chemistry, electromagnetic and optical materials. With the research development of inorganic-organic hybrid materials, peoples found that organic molecules can influence the nucleation and growth of inorganic compound, and control the microstructure of the inorganic framework. By the interaction of the interface between the organic molecules and inorganic components, the organic molecules can imprint the structure information to the inorganic framework and thus obtain a series of hybrid materials with novel structures and special properties. Recently, the various in structures of inorganic-organic hybrid materials has been greatly developed. However,design and synthesis of inorganic-organic hybrid materials directed by various properties is still a challenging project in this field. There are now four major classes of materials in which organic components exert a significant structural role in the control of the inorganic oxide microstructure. These materials are zeolites, mesoporous oxides of the MCM-41 class, biomineralized materials, microporous octahedral-tetrahedral or square-pyramidal-tetrahedral framework transition metal phosphates (TMPO) with entrained organic cations and dipodal organonitrogen-templated molybdenum/vanadium oxides. Taking into account of the international studies, we have focused our study on the influence of the changes caused by the coordination position or the distinct second metal atoms on the structure of inorganic-organic hybrid compound, synthesized and characterized a series of inorganic-organic hybrid compound with novel structures. Introducing the distinct second metal atoms into the V-O-P system, we have hydrothermally synthesized two new two-dimensional layerd vanadium phosphates, Ni(phen)(H2O)VO(H2O)(HPO4)2 (1) and Co(phen)(H2O)VO(H2O)(HPO4)2 (2), using phen as structural directional agent. Being characterized by single-crystal X-ray diffraction, the two compounds are isostructural and crystallize in the monoclinic system with P21/c space group with a = 14.3903(7) ?, b = 15.5232(6) ?, c = 7.3943(3) ?, β= 90.577(2) ?, V = 1651.7(2) ?3 for 1, and a = 14.3726(4) ?, b = 15.5078(5) ?, c = 7.3932(2) ?, β= 90.576(2) ?, V = 1647.77(8) ?3 for 2. The structure exhibits an unusual 4,12-membered rings oxovanadium phosphate (V-P-O) layer capped by [M(phen)]2+ complexes with phen groups projecting above and below into the interlamellar regions. Therefore, the bimetallic phosphate undulating layers extend into three-dimensional supermolecular arrays through a strong π-πstacking interaction of the phen groups between adjacent layers. Generally, the influence to the inorganic framework exerted by the second metal atoms is mainly caused by the difference of coordination capacity and coordination sphere of different atoms. Due to the Ni2+ and Co2+ atoms were inclined to exist in octahedra, so the inorganic framework structure of compound 1 and 2 is the same. Introducing three different bidentate organodiamine ligands into the V-O-P system, we have hydrothermally synthesized three inorganic-inorganic hybrid compound, [Cu(phen)]2(VO2)(H2O)2(H2PO4)2(PO4) (3) , [Cu(4,4'-bpy)(VO) (HPO4)(H2PO4)]2 (4) and [{Cu(2,2'-bpy)}2(VO)3(PO4)2(HPO4)]2·2H2O (5). Being characterized by single-crystal X-ray diffraction, compound 3 crystallizes in the Orthorhombic system with Pccn space group with a = 10.0756(4) ?,b = 12.7812(4)...