| 基于半刚性的4-羧基苯乙酸和富氮共配体组装的Zn(Ⅱ)/Cd(Ⅱ)配位聚合物的合成、结构和性质 |
| Zinc(Ⅱ) and Cadmium(Ⅱ) Coordination Polymers with Various Polynuclears Spaced by Semirigid 4-Carboxybenzeneacetate and Nitrogen-Rich Co-ligands: Syntheses, Structures and Properties |
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| 摘要: 采用溶剂热法合成了一系列Zn（Ⅱ）/Cd（Ⅱ）配位聚合物：{[Zn（cbaa）（bpmp）0.5（H2O）]·2H2O}n（1）、[Zn（cbaa）（bip）]n（2）、[Cd（cbaa）（Hizb）]n（3）和[Cd2（cbaa）2（itmb）（H2O）]n（4）（H2cbaa=4-羧基苯乙酸；bpmp=1，4-二（4-吡啶甲基）哌嗪；bip=3，5-双（1-咪唑基）吡啶；Hizb=2-（4-咪唑-1-基苯基）-1H-苯并咪唑；itmb=1-（咪唑-1-基）-4-（1，2，4-三唑-1-基甲基）苯）。X射线单晶衍射结果表明，半刚性的4-羧基苯乙酸和富氮辅助配体构筑形成了4个多样化拓扑结构的配位聚合物。化合物1和2是Zn（Ⅱ）配位聚合物：1是由2个Zn-羧酸盐链之间通过富氮配体桥连形成的一维梯形结构，而2是由Zn-羧酸盐链之间通过富氮配体拓展形成的二维单层结构；化合物3和4是Cd（Ⅱ）配位聚合物：3是由Cd-O无机链之间通过羧酸配体的桥连拓展形成的二维单层结构，富氮配体作为伸出层平面的悬臂仅仅起到结构修饰作用，而4则形成了Cd-羧酸盐空旷双层结构，富氮配体填充在层内空腔中，从而导致了致密双层结构的产生。另外，考察了4个化合物的热稳定性和光致发光性能。 |
| 关键词: 溶剂热合成 锌 镉 配位聚合物 荧光 |
| 基金项目: 国家自然科学基金（No.21571093）、河南省高校科技创新人才项目（No.14HASTIT017）、河南省高校科技创新团队项目（No.14IRTSTHN008）和河南省科技攻关计划（No.162102210304）资助。 |
| Abstract: A series of four Zn(Ⅱ)/Cd(Ⅱ)) coordination polymers, {[Zn(cbaa)(bpmp)0.5(H2O)]·2H2O}n (1),[Zn(cbaa)(bip)]n (2),[Cd(cbaa)(Hizb)]n (3) and[Cd2(cbaa)2(itmb)(H2O)]n (4) have been obtained by the solvothermal reaction of Zn(Ⅱ)/Cd(Ⅱ) acetate with semirigid 4-carboxybenzeneacetic acid (H2cbaa) and co-ligands, 1,4-bis(4-pyridyl-methy)piperazine (bpmp), 3,5-bis(1-imidazoly)pyridine (bip), 2-(4-imidazol-l-yl-phenyl)-1H-benzimidazole (Hizb) and 1-(imidazo-1-ly)-4-(1,2,4-trazol-1-ylmethyl)benzene (itmb). The single-crystal X-ray diffraction analyses show that four compounds feature various polynuclears spaced by 4-carboxybenzeneacetate and N-rich co-ligands and display various topology structures. Two zinc complexes are 1D ladder featuring Zn-carboxylate chains linked further by bpmp co-ligands for 1 and 2D monolayer containing Zn-carboxylate chains cross-linked further by bip co-ligands for 2, respectively. And two cadmium complexes exhibit 2D monolayer featuring Cd-O inorganic chains cross-linked further by cbaa carboxylates with Hizb co-ligands acting as pendent arms for 3 and 2D dense bilayer containing Cd-carboxylate open bilayer with itmb co-ligands encapsulated within the cavities for 4, respectively. The fluorescent properties and thermal stabilities of all these compounds have been investigated. |
| Keywords: 4-carboxybenzeneacetic acid zinc cadmium coordination polymers fluorescent properties |
| 投稿时间：2016-06-30 修订日期：2016-09-14 |
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| 鞠丰阳,李云平,李桂连,刘广臻,辛凌云,李晓玲.基于半刚性的4-羧基苯乙酸和富氮共配体组装的Zn(Ⅱ)/Cd(Ⅱ)配位聚合物的合成、结构和性质[J].无机化学学报,2016,32(10):1876-1884. |
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