| Since last century, design and synthesis of multy-functional metal-organic complexes have attracted tremendous interest for peculiar properties such as luminescence, molecular magnetism, gas adsorption, conductivity, catalysis, and so on. The intrinsic geometric preferences of metal centers and the various coordination modes of bridging organic linkers are vital factors in governing architectures.Considerable efforts have been devoted to the construction of intriguing coordination polymers based on multidentate N-donor building-blocks. Tetrazolate and their derivatives as five-membered N-heterocyclic azoles, are considered to be more suitable candidates for the construction of coordination networks through diverse chelating and/or bridging modes and can be deprotonated as anion to coordinate metal ions. Morever, conformational freedom of torsional C–C bonds allow them to adapt to the coordination environment of the metal ions.In this work, twenty-one complexes based on three flexible bistetrazole have been successfully obtained under solvothermal or temperature condition. The crystal structures, topological analysis, photoluminescence properties, thermogravimetric analyses, magnetic properties, photocatalytic performance of a portion of these complexes have also been investigated. The main points in this dissertation are summarized as follows:1. Three structural related flexible bistetrazole ligands [bis-?1H-tetrazol-5-ylmethyl?-amine?H3L1?, bis-?1H-tetrazol-5-ylethyl?-amine?H3L2? and1,5-bis?5-tetrazol?-3-thiapentane?H2L3?] were synthesized according to reference method and characterized by IR, 1H NMR. Besides, the photoluminescence properties of the ligands were investigated and discussed.2. Eleven bistetrazole-zinc(II)/cadmium(II) complexes based on the ligands H3L1 and H3L2, were obtained and structurally characterized, namely: [Zn?HL1??H2O?]n?1?,[Zn?HL1?]n?2?, {[Zn2?HL1?2?H2O?4]·2H2O}?3?, [Cd?HL1?]n?4?, [Cd3?HL1?2Cl2]n?5?,{[Cd2?HL1?2?H2O?4]·2H2O}?6?, {[Cd2?HL1?2]·H2O}-n?7?, [Zn?HL2?]n?8?,[Zn2?HL2?N3Cl]n?9?, [Cd?HL2??H2O?3]?10?, [Cd2?HL2??NO3??OH??H2O?]n?11?. The coordination modes and conformation of ligands have been explored. Structural analyses reveal that the flexible liands exhibit various coordination modes. The complexes 4, 5 and 7 exhibit three-dimentional frameworks?3-D? possessing infinite channels, complexes 1, 2, 8, 9 and 11 possess two-dimentional?2-D? net, and complexes 3, 6 and 10 show zero-dimentional?0-D? dinuclear or mononuclear structures. Besides, five kinds of topological structures of one 2-D sql net and four3-D sqc?bcu-x?tcj/hc?hxl nets were obtained. Furthermore,fluorescent emission,fluorescence lifetime, UV-vis diffuse-reflectance spectra and catalytic activities of the complexes 1–2 and 5–11 have also been investigated and discussed.3. Ten bistetrazole-copper(II)/cobalt(II)/manganese(II) complexes based on the ligands H3L1, H3L2 and H2L3, were obtained and structurally characterized, namely:[Cu2?HL1?2?H2O?2]?12?, [Cu?HL1??H2O?2]?13?, {[Co2?HL1?2]·TEA}?14?,[Co3?HL1?2?H2L1?2?H2O?4]n?15?, {[Mn2?HL1?2?H2O?4]·2H2O}?16?, [Cu?HL2??H2O?2]?17?, {[Cu5?HL2?2?ClO4?2?OH?4]·4H2O}n?18?,{[Cu5?HL2?2?SO4?2?OH?2?H2O?2]·5H2O}n?19?, [Cu?HL2?]n?20?,[Cu3?L3?2?OH?2?H2O?2]?21?. Complexes 12 and 16 display topological pcu and bcu-x nets, respectively, while the framework 4 and supramolecular network 5 exhibit topological sql net. The investigation of magnetic properties of complex 12?16?19?20 and 21 demonstrate dominant antiferromagnetic coupling existing in these complexes. |
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