Hydrothermal Synthesis And Characterization Of Structure Of Organic-inorganic Complexes Based On Tungstophosphate

In this thesis, five unprecedented organic-inorganic complexes based on tungsten phosphate have been hydrothermally synthesized by changing reaction materials and reaction conditions, and characterized by elemental analyses, IR, TGA, and single crystal X-ray diffraction. These new compounds are below:[PW11VO40{Co(phen)2H2O}2]·3H2O (1) in the space group P-1 of the triclinic system with a=10.965(5)?, b=13.330(5)?, c=13.645(5)?,α=69.257(5),β=71.394(5),γ=78.395(5), V=1758.91(2) ?3,Z=1.[PW11VO40{Zn(phen)2H2O}2]·3H2O (2) in the space group P-1 of the triclinic system with a=10.9448(4)?, b=13.3299(5)?, c=13.6522(5)?,α=69.1080(10),β=71.3230(10),γ=78.3400(10), V=1754.10(11) ?3, Z=1.[PW11VO40{Ni(phen)2H2O}2]·3H2O (3) in the space group P-1 of the triclinic system with a=10.973(2)?, b=13.307(3)?, c=13.602(3)?,α=69.30(3),β=71.18(3),γ=78.14(3), V=1749.0(6) ?3, Z=1.[Cu(C6H18N4)H2O]2 [Cu(C6H18N4)][ P2W18O62]·2H2O (4) in the space group P2(1)/c of the monoclinic system with a=14.1342(9)?, b= 20.4831(12) ?,c=28.7070(18) ?,α=90.00,β= 95.7860(10),γ=90.00,V= 8268.7(9)? 3,Z=4。C6H20Co3N4O30P4W4 (5) in the space group I4(1)/a of the Tetragonal system with a=17.1006(7)?, b=17.1006(7) ?,c=10.7525 (5) ?,α=90.00,β=90.00 ,γ=90.00,V=3144.4(2) ? 3,Z=22。Compounds 1 , 2 and 3 have the similar structure. The three compounds are composed of the mixed tungsten-vanadium polyoxoanion [PW11VO40]4- and one pair of opposite covalently linked [M(phen)2H2O]2+(M=Co 1,Zn 2,Ni 3) transition metal complex fragments, and a infinite 3D supramolecular framework is obtained via hydrogen-bonding interactions andπ-πstacking contacts .Compound 4 is a Wells-Dawson type heteropolytungstate derivative with [Cu(C6H18N4)H2O]2+ and [Cu(C6H18N4)]2+ as cations, and a infinite 3D supramolecular framework is obtained through hydrogen-bonding interactions and Vander Walls forces. Compound 5 is a novel complex of three dimensional polyoxotungstate framework.The protonated ethylenediamine molecules act as charge-compensation cations in the compound. From these hydrothermal experiments, we found that the type and ratio of reaction materials , reaction temperature, reaction times and pH value have importantly influenced on the final crystal product and yield, and pH value is the crucial factor.