Syntheses,Structures And Properties Of Coordination Complexes Based On Thiadiazole Or Terphenyl Tetracarboxylate Ligands

In this thesis,2-mercapto-5-methyl-1,3,4-thi adi azole(MMT),2-mercapto-1,3,4-thiadiazole(MT),amino-5-mercapto-1,3,4-thiaoldiaze(AMT),5-(methylthio)-1,3,4-thiadiazole-2-thiol(S-MMT)have been selected as the ligands to obtain thirteen new polynuclear oxygen clusters based on Co? and Ni? ions.[1,4':1"-terphenyl]-2',4,4",5'-tetracarboxylic acid(H4L)have been selected as the main ligands,and bis-pyridyl ligands have been used as the auxiliary ligands to react with different transition metals,obtaining ten new coordination polymers.Twenty-three new complexes have been synthesized and characterized by single-crystal X-ray diffraction,elemental analyses,IR and X-ray powder diffraction(XRPD)patterns.In addition,the TG,fluorescent properties,electrochemical behaviors,adsorption properties and photocatalytic properties of some complexes have been studied.1.Using the thiadiazole ligands(MMT?MT?AMT and S-MMT),a series of polynuclear clusters based on Co? and Ni? ions have been synthesized in the solvothermal conditions and structurally characterized.Study on the roles of different reaction conditions,the coordination modes and the different substituent groups of the ligands for structures of complexes.[Co20(MT)12(?3-OH)23(?3-O)(SO4)(CH3O)]·2EtOH(2)[Co20(AMT)11(MT)(?3-OH)22(?3-O)2(SO4)(H20)]·EtOH-4H20(3)[Co3(S-MMT)3(?3-OH)(DEA)2](DEA= Diethanolamine)(4)[Ni(AMT)2(EDA)2]2(EDA= Ethylenediamine)(5)[Ni4(AMT)6(?3-OH)2(H20)6](6)[Ni4(AMT)6(?3-OH)2(H2O)6]·4H2O(7)[Ni2(AMT)3(?3-OH)(H2O)3]-H2O(8)[Co10(MMT)6(?3-OH)12(SO4)0.5](SO3NH2)(9){[Ni20(MMT)12(?3-OH)24(S04)](SO3NH2)2}2(10)Complex 1 that has been reported by our group presents a homometallic Co? cluster containing the a-Keggin polyoxometalate structure.Complex 2 features a cobalt cluster including the a-Keggin-type polyoxoazocobaltate ?Co12} core,capped by seven octahedral Co?ions and one square-pyramidal Co? ion.Complex 3 possesses the semi-open square-pyramidal-based {Co10} core,and ten octahedral Co? ions are distributed around the core cluster.Complex 4 is a ?Co6} cluster containing two trinuclear units.Complexes 5-8 have the same reactants,but the different reaction conditions lead to the differences of the structures.Complex 5 is a mononuclear,and complex 6 is a Ni4} cluster.In complexes 7-8,the differences of the lattice water molecules lead to the differences of the supermolecule structures.Complex 9 is a {Co20} cluster containing non-saturated Keggin-type {C012} core.Complex 10 is a {NM20} cluster containing saturated Keggin-type core.In complexes 1-3,although the ligands coordinating with Co? ions are the thiadiazole ligands,the different substituent groups of the organic ligands lead to the differences of the final homometallic Co? clusters.Moreover,photocatalytic properties show that complexes as the potential photoactive materials have the selectivity for degradation of some organic dyes.2.Using the two thiadiazole ligands(MMT and MT)and two transition metals,four polynuclear clusters have been synthesized in the solvothermal conditions and structurally characterized.Study on the roles of the coordination abilities from different thiadiazole ligands and the different molar ratios of metal reactants for structures of complexes.[Co2o(MMT)12(?3-OH)2l(?3-O)3](SO3NH2)·3EtOH(11)[Co2o(MT)12(?3-OH)22(?3-O)2(SO4)]-4EtOH(12)[Ni12Co8(OH)24(MMT)12(S04)](N03)2-8H20(13)[Ni4Co16(OH)24(MMT)12(S04)](N03)2(14)Complex 11 is a {Co20} cluster including {Co12} nanocage and eight Co? ions.Different from complex 11,complex 12 is a {Co20} cluster containing a[SO4]2-,two {Co8}clusters and four square-pyramidal Co? ions.Complex 13 is a {Ni12Co8} mixed metal clusters containing {Ni12} core and eight Co? ions.Complex 14 is a {Ni4Co16 mixed metal clusters containing mixed {Ni4Co8} core and eight peripheral Co? ions.Moreover,photocatalytic properties show that complexes have the selectivity for degradation of some organic dyes.3?Using the main ligand H4L and different bis-pyridyl ligands,ten coordination polymers with different structural features have been hydrothermally or solvothermal synthesized and structurally characterized.Study on the roles of metal ions and the coordination modes of ligands for sructures of complexes.[Mn(H2L)]n(15){[Ni3(L)(?3-OH)2(H2O)4]2·3H2O}?(16){[(CH3)2NH2]2[Zn(L)]·2DMF}n(17)[Co(H2L)(bpe)2]n(18)[Co2(L)(bpmp)(H2O)]n(19)[Co(H2L)(bpfp)(H2O)2]n(20){[Ni(H2L)(bpe)(H2O)2]·2H2O}n(21)[Ni(L)0.5(bpmp)0.5]n(22){[Cd(H2L)(bpe)0.5(H2O)2]·0.5(bpe)}n(23){[Cd2(L)(bpfp)0.5]·H2O}n(24)Complex 15 represents a 6-connected {412·63} framework,which contains ID stair-type chain and 2D layer derived from the carboxyl groups with different coordination modes and the metal Mn? ions.Complex 16 displays the complicated topology with{411·612·85}{42·6}{43·63}{43}{44·6·}{48·6·8},in which Ni-O chains consisting of different Ni-Ni units play an important role in the whole framework.In complex 17,the wave-like and "H"-like ID chains link each other to create the 3D architecture with {42·84} topology.Complex 18 represents a 2D coordination layer consisted of the metal Co? ions and H2L ligands,and the monodentate bpe ligands hang both sides of the network.Complex 19 is a(4,6)-connected 3D framework based on Co-L 2D sheets.Complex 20 possesses a 2D(4,4)network containing the "H"-type ID Co-H2L chains and 1D Co-bpfp zigzag chains.Complex 21 is similar with complex 20 except for containing the 1D Ni-bpe straight chains.Complex 22 displays a 3D framework with the symmetrical polygonal windows.Complex 23 exhibits a 2D {63} layer including hexagonal grids,and some non-coordinated bpe ligands exist in the network.Complex 24 is a 3D complicated {415·613}2{42·63·8}{47·63}4 framework.Moreover,photocatalytic properties for the degradation of organic dye methylene blue(MB)are studied.