基于阴离子调控策略的Co(Ⅱ)配位聚合物的合成、晶体结构及荧光性质  

Syntheses, Crystal Structures and Fluorescence Properties of Co(Ⅱ) Coordination Polymers Based on Anion Regulation Strategy

作　　者：李响 赵怀安 苏剑 程军妍 王鹏[1] LI Xiang;ZHAO Huai-An;SU Jian;CHENG Jun-Yan;WANG Peng(College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao, Shandong 266590, China;State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China;College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, China)

机构地区：[1]山东科技大学化学与环境工程学院,青岛266590 [2]南京大学化学化工学院配位化学国家重点实验室人工微结构科学与技术协同创新中心,南京210023 [3]山东师范大学化学化工与材料科学学院,济南250014

出　　处：《无机化学学报》2019年第1期109-115,共7页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21101099)资助项目

摘　　要：以三键桥联吡啶类配体2,6-二(3′-吡啶乙炔基)-4-甲基苯胺(L)为配体,在常温混合溶剂(二氯甲烷-甲醇)中分别与CoCl_2、Co(SCN)2通过自组装反应,获得了一维及二维配位聚合物[Co(L)Cl_2]_n(1)及[Co(L)_2(SCN)_2]_n(2),通过红外、元素分析、X射线单晶衍射等检测手段对所合成的配合物进行了结构表征。对比1和2的单晶结构可以发现,配体L在配位聚合物1和2中的配位取向及结构相似,不同的是Co(Ⅱ)离子的配位数受配位阴离子的影响而不同:配位聚合物1中四配位的Co(Ⅱ)通过2个配体的相互连接呈现一维的弯曲链状结构,而配位聚合物2中六配位的Co(Ⅱ)则通过4个配体的相互连接得到二维的平面结构。2个配合物中均存在氢键及π-π相互作用。通过粉末衍射证明了配位聚合物1和2为单一晶相,其固态下的荧光测试显示,二者的荧光均减弱,并相对于配体L有红移(1)及蓝移(2)。Two coordination polymers [Co(L)Cl2]n (1) and [Co(L)2(SCN)2]n (2) were obtained by using 4-methyl-2,6-bis(pyridin-3-ylethynyl) aniline (L) and Co(Ⅱ) salts in CH2Cl2/MeOH mixed solvent under room temperature. The complexes 1 and 2 were characterized by IR, elemental analysis and X-ray single crystal diffraction. The structural analysis revealed that complex 1 has 1D chain structure and 2 has 2D plane structure. The reason of the structure difference was anion choice because the L in both of the coordination complexes adopts almost same trans-N,N donor configuration. Complex 1 has four-coordinated Co(Ⅱ)) which coordinated to two L molecules, while complex 2 has six-coordinated Co(Ⅱ) which coordinated to four L molecules. The XRD and fluorescence property of two complexes were investigated. Compared to the emission spectrum of L, the emission maximum of the complex 1 was red shift and 2 was blue shift. CCDC: 1869513, 1;1869512,2.

关 键 词：吡啶配体 阴离子调控 Co(Ⅱ)配位聚合物 晶体结构 

分 类 号：O914.812[理学]