The Template Effect Of N-containing Organic Di-and Multi-Cations Synthesis, Structures And Properties Of The Oriented D¹⁰Metal-based Networks

Pseudorotaxane has gained considerable attention in recent yeas due to their photochemical property, molecular recognition and energy exchange. Dications are still worth investigation and research about multications still remains rare in the fabrication of inorganic-organic hybrids. Especially the multications which present low charge such as trications and tetracations induce relatively simple multivalent interactions with inorganic moieties, which make them appropriate for deep investigation. This thesis focuses on the analysis of the effect stoppers in dications or multications have on (pseudo)halide-based mineral phase. The stoppers used herein are pyridinium,1-methylimidazole,1,3-dimethylimidazole and most of the inorganic frameworks oriented by cations with those stoppers feature2-3D pseudorotaxane.The author synthesized17hybrids from methanol/N, N-dimethyl fomamide system via self-assembly reaction which had never been reported.The reaction between CuI, AgI, or AgBr and dmb·Cl2[α, α’-di(3-methyl imidozole-1-yl) benzene dichloride] or ddb·Cl2[α, α’-di(2,3-dimethyl imidozole-1-yl) benzene dichloride] gives6hybrids. Complexes{[dmb]2[Cu4I8]}-2DMF(1),{[dmb]2[Ag2I4]}n (3) and{[dmb]2[Ag2Br6]}(5) present the relatively simple tetrameric,1D or dimeric structure. While complexes{[ddb]2[Cu4I6]}n(2),{[ddb]2[Ag2I6]}n(4),{[ddb]2[Ag4Br6]}n(6) present the same composite double-chains with much more metal-metal interactions.The reaction of CuSCN with1-iBV-Br [1-isobutyl-4,4’-bipyridinium) bromide] or iBV-2Br [1,1’-diisobutyl-4,4’-bipyridinium dibromide] gives complexes{(1-iBV)[Cu2(SCN)3]}n (7) and{(iBV)[Cu2(SCN)4]}n (8). Both of them feature honeycomb-like pseudorotaxanes with corresponding cations trapped in.When CuSCN reacted with tbp-Br3[1,3,5-tri(N-pyridiniummethyl) benzene tribromide], tbmp-Br3[1,3,5-tri(N-pyridiniummethyl)-2,4,6-trimethylbenzene tribromide], or tebp-Br4[1,2,4,5-tetra (N-pyridiniummethyl) benzene tetrabromide], the author obtained compound9-12. Complexes [Cu(SCN)2]3(?)(tbp)}n(9) and {[Cu(SCN)2]8(?)(tebp)2}n(11) give3D pseudorotaxane frameworks, while compounds {[Cu2(SCN)5]8(?)(tbmp)}n (10) presents2D pseudorotaxane networks. Arised from the same mother solution with10,{(tebp)[Cu2(SCN)6]}(12) only gives dimeric framework though made of the same materials.The author synthesized compound13-17via the reactions of CuSCN with tbi-Br3[1,3,5-tri (N-1-methylimidazolemethyl)benzene tribromide], tbmi-Br3[1,3,5-tri (N-1-methylimidazolemethyl)-2,4,6-trimethylbenzene tribromide], or tebi-Br4[1,2,4,5-tetra (N-1-methylimidazolemethyl)benzene tetrabromide]. Complex13gives3D network and complex{(tbmi)[Cu2(SCN)s]}n(14) presents2D network. Similar with complex14structurally, complexes{(tebi)[Cu (SCN)2]4}n (15) and{[Cu (SCN)2]4(?)(tebi)}n (16) are isomers growing from the same mother solution. The reaction of AgSCN with tbmi-BF4gives compound17.Almost all compounds were further characterized with IR spectra, thermal robustness and UV-vis spectra in solid state.