| The aim of this thesis is to construct a series of coordination polymers with various structures based on several isomers of multidentate N-donor ligands1-((1H-1,2,4-triazol-1-y1)methy1)-3,5-bis(pyridy1)-1,2,-triazole (tmbpt), polycarboxylates/polyoxometalates anions and transition metal ions under hydrothermal conditions. The synthesis conditions, types of topological structures, effects of the structures of organic ligands and the types of metal ions and anions on the structures of the compounds, and the relationship between structures and properties of the compounds have been investigated in detail.Twenty-six coordination polymers have been hydrothermally synthesized and characterized by infrared spectra (IR), elemental analyses and thermogravimetric (TG) analyses. Moreover, the luminescent properties and photocatalytic behaviors of the compounds have also been investigated.1. The combination of multidentate N-donor ligand1-((1H-1,2,4-triazol-1-yl)methy1)-3,5-bis(4-pyridyl)-1,2,4-triazole (4,4’-tmbpt) and auxiliary aromatic polycarboxylic acids (o-H2bdc=1,2-benzenedicarboxylic acid, m-Hbdc1,3-benzenedicarboxylic acid,5-OH-H2bdc=5-hydroxy-1,3-benzenedicarboxylic acid,1,2,3-H3btc=1,2,3-benzenetricarboxylic acid and p-H2bdc=1,4-benzenedicarboxylic acid) in the presence of Cd(â…¡) and Zn(â…¡) ions provides eight coordination polymers. Compounds1,3and7display different2Dâ†'3D inter digitated structures. Compound2shows a3D6-connected framework with (412·63) topology. Compound4reveals a3D (3,4,8)-connected net based on hexanuclear units. Compounds5and8are isostructural and display3D (3,9)-connected frameworks based on trinuclear units. Compound6exhibits an unusual2Dâ†'3D polythreaded architecture.[Cd(4,4’-tmbpt)(o-bdc)(H2O)]·5.25H2O (1)[Cd(4,4’-tmbpt)(m-bdc)](2)[Cd(4,4’-tmbpt)(5-OH-bdc)](3)[Cd5Na2(4,4’-tmbpt)2(1,2,3-btc)4(H2O)3.5]·6.5H2O (4)[Cd3(4,4’-tmbpt)(1,2,3-btc)2(H2O)2]·H2O (5)[Zn(4,4’-tmbpt)(m-bdc)](6)[Zn3(4,4’-tmbpt)2(p-bdc)3]·5.5H2O (7)[Zn3(4,4’-tmbpt)(1,2,3-btc)2(H2O)2]·H2O (8)2. The mixed ligands of1-((1H-1,2,4-triazol-1-yl)methyl)-3-(3-pyridyl)-5-(2-pyridyl)-1,2,4-triazole (2,3’-tmbpt) and 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole (3,3’-tmbpt) with distinct aromatic polycarboxylic acids (1,3,5-H3btc=1,3,5-benzenetricarboxylic acid and H4btec1,2,4,5-benzenetetracarboxylic acid) in the presence of Zn(â…¡) ions afford eight coordination polymers with various structures under hydrothermal conditions. Compounds9and14display1D chain structures. Compound10shows a3D2-fold interpenetrating CdSO4-type framework. Compound11reveals a2D2-fold interpenetrating square layer (sql) structure. Compound12exhibits a3D2-fold interpenetrating framework with (63)(69-8) topology. Compound13shows a non-interpenetrating3D framework with (83)(85-10) topology. Compound15has a2D layer structure. Compound16displays a3D2-fold interpenetrating framework with (4·62)(42·68·85) topology.[Zn(2,3’-tmbpt)(m-bdc)(H2O)](9)[Zn(2,3’-tmbpt)(m-dc)](10)[Zn(2,3’-tmbpt)(m-bdc)]·H2O (11)[Zn2(2,3’-tmbpt)(1,3,5-btc)(OH)]·0.5H2O (12)[Zn(2,3’-tmbpt)(btec)o.5]·2H2O (13)[Zn(3,3’-tmbpt)(o-bdc)]-H2O (14)[Zn(3,3’-tmbpt)(/m-bdc)(H2O)]·H2O (15)[Zn2(3,3’-tmbpt)(1,3,5-btc)(OH)(H2O)](16)3. The reactions of3,3’-tmbpt,1-((1H-1,2,4-triazol-1-yl)-methyl)-3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole)(3,4’-tmbpt) and4,4’-tmbpt with Ag(I) and Cd(II) ions with the help of5-(4’-carboxybenzyloxy)isophthalic acid give four highly connected coordination compounds containing metal clusters. Compound17features a3D (3,12)-connected net based on heptanuclear [Ag7(COO)7] units. Compound18displays a3D (3,4,10)-connected net constructed by tetranuclear [NaCd3(μ3-OH)(COO)5] units. Compound19exhibits a3D (3,4,8)-connected net based on binuclear [Cd2(COO)2] units. Compound20is a3D binodal (3,9)-connected framework constructed by trinuclear [Cd3(COO)4] units.[Ag7(4,4’-tmbpt)(HL)2(L)(H2O)](17)[NaCd3(4,4’-tmbpt)(L)2(OH)]-H2O (18)[Cd3(3,3’-tmbpt)2(L)2(H2O)2]-3.5H2O (19)[Cd3(3,4’-tmbpt)2(L)2(H2O)]·1.5H2O (20)4. Six coordination polymers based on multidentate N-donor ligands2,3’-tmbpt,1-((1H-1,2,4-triazol-l-yl)methyl)-3-(4-pyridyl)-5-(2-pyridyl)-1,2,4-triazole)(2,4’-tmbpt),3,3’-tmbpt and3,4’-tmbpt, octamolybdates and Ag(I) ions have been synthesized under hydrothermal conditions. Compound21displays a rare3D (3,4,8)-connected net with (4·82)(42·84)(43·820·105) topology. Compound22shows a3D (4,6)-connected self-catenated framework with (64-82)(42-63-82)(42-68-84-10) topology. Compound23is a scarce3D framework based on two different kinds of [Mo8O26]4-isomers. Compound24exhibits a3D framework constructed by silver-organic sheets and the rare [ε-Mo8O26]4-anions. Compound25shows an interesting1Dâ†'2D polythreaded structure. Compound26has a2D layer structure, which is linked by the hydrogen bonds to form a3D supramolecular architecture.[Ag2(2,3’-tmbpt)(β-Mo8O26)0.5](21)[Ag2(2,4’-tmbpt)2(α-Mo8O26)0.5(H2O)0.5]·2H2O (22)[Ag3(3,3’-tmbpt)2(α-H2Mo8O26)0.5(β-Mo8O26)0.5]·3.5H2O (23)[Ag2(3,3’-tmbpt)(ε-Mo8O26)0.5]·1.75H2O (24)[Ag2(3,4’-tmbpt)2(β-Mo8O26)0.5]·0.5H2O (25)[Ag(3,4’-Htmbpt)(β-Mo8O26)0.5](26)... |
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