Syntheses,Structures And Luminescence Properties Of Outer-bidentate N-containing Ligand Of Cuprous Bromide Coordination Polymers

Organic-inorganic hybrids promise the properties of both organiccomponent and inorganic component, so they have attractedconsiderable attention. Because of the rich coordination modes andgeometry of Cu（Ι） and halide anion, cuprous halides presentstructural diversity. In this paper, we synthesize a series of clusteror chain based cuprous bromide coordination polymers. Duringstudying cuprous bromide cluster based compounds, we performedalong a main line, namely: cuprous bromide anionic cluster→cuprous bromide anionic cluster and cationic cluster in the form ofcocrystallization→cuprous bromide cationic cluster. We found thattemperature plays a vital role in the forming of target products. Thethesis is mainly divided into four chapters:Chapter one, as a preface of the dissertation, mainly includesthree parts. One is a brief introduction to the structure and design ofmetal cluster-based high conjunction metal-organic frameworks.The other is the development and current studies of cuprousbromide cluster-based coordination polymers. The last part is thefluorescent properties of cuprous halides.In chapter two, under hydro（solve）thermal condition, by usingcopper bromide, DABCO and auxiliary ligand, we prepared a Cu₄Br₆^2– anionic cluster-based compound. Each cluster connects with fourDABCO groups by Cu-N bonds and two of the four DABCO groups areprotonated. These clusters are packed in a body centred cubicmode into 3D supramolecular array. By adjusting temperature,solvents and molar ratio, a cocrystallized compound of cuprousbromide anoinic and cationic cluster-based 3D network wasobtained. The first one is a cocrystallized compound of cluster[Cu₄Br₆（DABCO）₄] and 3D body centred cubic [Cu₈Br₆（DABCO）₄]_n, andthe stoichiometry is 0.76:0.24, namely:[Cu₄Br₆（HDABCO）₂（DABCO）₂]_0.76[Cu₈Br₆（DABCO）₄]_0.24; The second one is a cocrystallized com-pound of cluster [Cu₄Br₆（DABCO）₄] with different tropIsm and 3Dbody centred cubic [Cu₈Br₆（DABCO）₄]n, and the stoichiometry is0.18:0.44:0.38,namely:[Cu₄Br₆（HDABCO）₂（DABCO）₂]_0.18Cu₄Br₆（HADBCO）₂（DABCO）₂]_0.44[Cu₈Br₆（DABCO）₄]_0.38. Finally, by further adjusting te-mperature and changing the kind of solvents, an eight-connectedCu₈Br₆²⁺cationic cluster based 3D body centered cubic cationicframework was obtained. Deduced from IR spectrum and startingmaterial, the charge balance of the framework is achieved byformate generated by decomposing of DMF under hydrothermalcondition. Each cluster is connected to eight neighbors via bridgedDABCO ligands to form cationic framework with channel filled byHCOO–and disordered solvents.In chapter three, under hydro（solve）thermal condition, by usingcopper bromide and bpp, two chain based cuprous bromidecompounds 7 and 8 have been obtained. 7 contains a cuprousbromide chain. Through noclassical N-H···Br hydrogen bond-intera-ction between chain and protonated bpp, compound 7 forms a 2D supermolecular layer. 8 is a mixed-valence Cu（Ι/Ⅱ） compound, and itcontains a cuprous bromide rhomboid aggregate chain and isolatedCu^â…¡Br₄^2-. Through noclassical N-H···Br hydrogen bond-interactionbetween them and protonated bpp, compound 8 forms a 3Dsupermolecular net. Finally, by using copper bromide and DABCO,we obtain a six-connected Cu₂₃Br₂₃neutral cluster-basted 3Dcuprous bromide framework. For the partial protonization of DABCO,there also exist noclassical N-H···Br hydrogen bond- interaction.In chapter four, a concise conclusion is drawn and a perspectiveof this work is expected.