项目名称: 配体的原位合成制备功能无机配位聚合物材料
项目编号: No.21271083
项目类型: 面上项目
立项/批准年度: 2013
项目学科: 数理科学和化学
项目作者: 于杰辉
作者单位: 吉林大学
项目金额: 80万元
中文摘要: 本课题申请人拟利用四种配体间的原位反应合成新型无机功能配位聚合物材料:包括(I)利用有机酸与水合肼间的水热原位酰胺化反应合成新的金属?酰肼配位聚合物;(II) 利用N杂环配体与醇溶剂在有酸和碘离子存在的条件下的原位N-烷基化反应合成新的N杂环配体衍生物模板的铅碘酸盐、铜碘酸盐以及镉碘酸盐;(III) 利用硫氰根与亲核试剂间的加成反应合成新的有机硫配体修饰的金属卤?拟卤配位聚合物;(IV)利用有机二胺、叠氮酸钠以及原甲酸三乙酯间的原位反应合成1-取代双四唑桥联的金属卤素或拟卤素簇聚物,尤其是亚铜卤素簇或拟卤素簇聚物。通过对未经原位反应的情况的研究考察配体的原位反应对晶体的生长的影响,以及对产物结构的影响。对所合成的系列无机配位聚合物进行荧光性能研究,建立结构与性能间的经验关系,并利用密度泛函理论(DFT)计算探讨配合物的发光机理。
中文关键词: 原位酰化;原位N-烷基化;原位亲核加成;荧光;I2吸附
英文摘要: Employing four types of ligand in situ reactions to prepare novel functional inorganic coordination polymer materials including (i)the hydro(solvo)thermal acylation reactions between organic polycarboxylic acids and hydrazine hydrate to prepare the metal-mono(di)acylhydrazidate coordination polymers; (ii)the solvothermal N-alkylation reactions between N-heterocyclic ligands and alcohol solvents in acidic KI solutions to prepare derivate-templated iodometallates (M2+ = Pb2+, Cd2+, Cu2+);(iii)the addition reactions between inorganic SCN- group and organic nucleaphilic reagents to prepare metal halides/thiocyanates modified by new organic S ligands; (iv) the hydro(solvo)thermal in situ reactions between organic diamine molecules, sodium azide and triethyl orthoformate to prepare new metal halides/thiocyanates bridged by organic 1-substituted momo/ditetrazole molecules. The non in situ situations were also investiated in this project,in order to reveal the effects of the ligand in situ reactions towards the crystal growth and the networks structures of the products. Investigating the photoluminescence properties of all the obtained coordination materials, constructing the experience relationship between the structures and the properties, and exploring the luminescence mechanism of the materials by the desity functio
英文关键词: in situ acylation;in situ N-alkylation;in situ nucleophilic addition;photoluminescence;I2 adsorption