Synthesis,structures And Properties Of Novel Cu(Ⅰ)/Ag(Ⅰ) Functional Supramolecular Compounds Based On Nitrogen Heterocyclic Cations

With the development of the supramolecular chemistry,more and more people have paid attention to synthesizing the supramolecular polymers which have some functions instead of exploring the structure of them.There are a variety of nitrogen heterocyclic cations which can conduct the structures of a series of Cu（Ⅰ）/Ag（Ⅰ）halide/pseudohalide supramolecular polymers which have novel structure and special optical,electric,magnetic,semiconductive and photocatalytic performance.In this thesis,a series of divalent cations as template agents were synthesized and reacted with Cu（Ⅰ）/Ag（Ⅰ）halide/pseudohalide via slow evaporation approach at room temperature.Finally,nine novel supramolecular polymers were obtained.In addition,we explored the structures and the properties of compounds 1-9 by a variety of techniques.Firstly,we regarded 1,4-bis[（3,5-lutidine）-N-methylene]benzene dibromide and 1,4-bis[（4-picoline）-N-methylene]benzene dibromide as template agents to reacting with Cu（Ⅰ）/Ag（Ⅰ）halide/pseudohalide and compounds 1-6 were obtained.They were {（BLMB）_0.5[Cu（SCN）₂]}_n（1）,{（BPMB）_0.5[Cu（SCN）₂]}_n（2）,{（BPMB）[CuBr₃]}_n（3）,{（BPMB）[HgI₄（H₂O）_0.66]}_n（4）,{（BPMB）[Cu₂I₄]}_n（5）and {（BPMB）₂[Ag₄I₈]}_n（6）.We analyzed the structures of compounds 1-6 by X-ray single-crystal diffraction,infrared spectroscopy（IR）and elemental analysis and characterized the properties of compounds 1-6 by fluorescence spectrum and ultraviolet-visible（UV-vis）absorption spectrum.The results indicated that compound 1 has a 2D polypseudorotaxane structure;Compound 2 displays a 1D chain structure.Compounds 3 and 4 are the mononuclear structures;Compounds 5 and 6 have the multinuclear cubane structures.Compounds 1-6 showed good photocatalytic abilities for methylene blue（MB）irradiated by visible light.The effective detection of Fe³⁺ was performed by compounds 1-6 as fluorescent sensors.Then we employed bivalent cations 1,2-bis（4-aminopyridine）ethane dibromide,1,3-bis（4-aminopyridine）propanedibromide and 1,4-bis（4-aminopyridine）butane dibromide as template agents to reacting with Cu（Ⅰ）/Ag（Ⅰ）halide/pseudohalide and compounds 7-9 were obtained.They were {（BAPE）_0.5[Cu（SCN）₂]}_n（7）,{（BAPP）[Cu₂（SCN）₄]}_n（8）and {（BAPB）_0.5[Cu（SCN）₂]}_n（9）.The results showed that compounds 7 and 9 have 2D polypseudorotaxane structures.Compound 8 is a 3D network structure.Compounds 7-9 showed good photocatalytic abilities for methylene blue（MB）and rhodamine B（RhB）irradiated by visible light.