两个二维镉基配位聚合物的合成及其性质  

Synthesis and Properties of Two 2D Cadmium(Ⅱ)-based Coordination Polymers

作　　者：毛青青 王晓阳 王云飞 朱成峰 张艳华[2] 

机构地区：[1]合肥工业大学,安徽合肥230009 [2]安徽国防科技职业学院,安徽六安237011

出　　处：《合成化学》2017年第11期916-922,共7页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(21401037);安徽省自然科学基金资助项目(1508085QB26);合肥工业大学2015年大学生创新训练项目(201510359048);安徽高校人文社会科学研究重点项目(SK20160206)

摘　　要：以廉价易得的3,5-二溴甲苯和1,3,5-三溴苯为初始原料,通过两步反应设计合成了二种含120°夹角的刚性羧酸桥联配体L_1-H_2(2a)和L_2-H_2(2b);并利用水热-溶剂热反应与镉离子合成了两种新颖的镉基配位聚合物[CdL_1]·DMF·H_2O(3a)和[CdL_2]·DMF·H_2O(3b),其结构经X-射线单晶衍射、X-射线粉末衍射和IR表征。3a和3b均属于正交晶系,Pbca空间群,中心金属镉离子采取扭曲的五角双锥配位构型,两个镉离子所形成的双核Cd2(OAc)2单元与周围的四个配体相互连接而成二维的网状结构。TGA显示配合物3a和3b的网络结构的热分解温度分别为355℃和360℃,具有较好的热稳定性。配体2a和2b的荧光光谱显示最大发射波长分别位于415和383 nm处,而3a和3b的最大发射波长分别位于362 nm和357 nm处,发生了明显蓝移。Two rigid bridging ligands, L1 -H2 （2a） and L2-H2 （2b）, were synthesized using 1,3-dibro- mo-5-methylbenzene and 1,3,5-tribromobenzene as starting materials, respectively, which were e ployed to prepare two Cd-based coordination polymers, [ CdL1 ] · DMF · H2O （3a） and [ CdL2 ]· DMF · H2O （3b）. The structures were characterized by IR, TGA, single and powder X-ray diffrac- tion. 3a is isostructural with 3b, and they crystallize in the orthorhombic space group Pbca. The Cd （Ⅱ） centers adopt a distorted pentagonal bipyramid geometry. The dinuclear Cd2 （OAc）2 units con- structed by two Cd （Ⅱ） ions are linked by four ligands to generate a two dimensional network. Thermo- gravimetric analysis showed that 3a and 3b are thermally robust with network decomposition tempera- ture up to 355 ℃ and 360 ℃, respectively. The fluorescence spectra of 2a and 2b in solid state at room temperature showed their major emission peaks located at approximately 415 and 383 nm, respec- tively. Compared with the two free ligands, the fluorescence spectra of 3a and 3b showed a marked blue shift, with their major emission peaks centered at 362 nm and 357 nm, respectively.

关 键 词：溴甲苯 桥联配体 镉离子 配位聚合物 溶剂热合成 晶体结构 

分 类 号：O614[理学—无机化学] O76[理学—化学]