基于配位键和次级作用力协同效应构建的两个Co(Ⅱ)/Cd(Ⅱ)配位超分子网络的结构及荧光性质  

Structures and Luminescence Property of Two Co(Ⅱ) and Cd(Ⅱ) Supramolecular Coordination Networks Created via Synergistic Effect of Coordination Bonds and Secondary Interactions

作　　者：任永合 李鲁超 丁琦晖 黄永清 赵越 REN Yong-He;LI Lu-Chao;DING Qi-Hui;HUANG Yong-Qing;ZHAO Yue(College of Chemical and Biological Engineering,Shandong University of Science and Technology,Qingdao,Shandong 266590,China;State Key Laboratory of Coordination Chemistry,School of Chemical and Chemical Engineering,Nanjing University,Nanjing 210023,China)

机构地区：[1]山东科技大学化学与生物工程学院,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,南京210023

出　　处：《无机化学学报》2021年第11期2047-2058,共12页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21201111)资助。

摘　　要：以3-羧基-1-(4-羧基苄基)吡啶溴酸盐((H_(2)L)Br)分别与Co(Ⅱ)和Cd􀃭金属盐反应,制备了2个配合物[Co(L)_(2)(H_(2)O)_(4)]·2H_(2)O(1)和[Cd(L)_(2)(H_(2)O)]·3H_(2)O(2)。晶体结构分析揭示配合物1是一个中性的单核配合物,其拥有丰富的并可作为超分子合成子的氢键和π-π作用力组分。对于1,单核的[Co(L)_(2)(H_(2)O)4]实体首先通过氢键形成具有孔道结构的二维层,该二维层进一步通过π-π堆积作用形成三维的多孔配位超分子。配合物2具有一维的“之”字形链状结构,该链通过悬挂的L配体之间的π-π作用力形成一维梯形结构。该一维梯形链进一步通过梯形边之间存在的2种π-π堆积作用形成波浪状的二维层。二维层进一步通过8种类型的O—H…O氢键连接形成三维的超分子结构。根据拓扑的观点,配合物2中的一维链采取胶合板排列。此外,配合物2显示了强的紫外荧光发射,平均寿命为2.54 ns。Two complexes with chemical formulas[Co(L)_(2)(H_(2)O)_(4)]·2H_(2)O(1)and[Cd(L)2(H_(2)O)]·3H_(2)O(2)were obtained by the reaction of 3-carboxy-1-(4-carboxybenzyl)-pyridinium bromide((H_(2)L)Br)with corresponding Co(Ⅱ)and Cd(Ⅱ)metal salts.Crystal structure analysis reveals that 1 is a neutral mononuclear complex,which possesses abundant hydrogen bond andπ-πinteraction components and can be used as supramolecular synthons.In the case of 1,mononuclear[Co(L)2(H_(2)O)_(4)]coordination entities are first joined via hydrogen bonding to produce channel-structured 2D layers,which are further stacked viaπ-πstacking effect in an interdigitating fashion,generating a 3D porous supramolecular assembly.2 features a polymeric 1D zigzag chain structure,which is connected viaπ-πinteractions between pendent L ligands,resulting in the formation of 1D ladder chains.Such 1D ladder chains are further combined into wave-like 2D sheets via another two kinds ofπ-πstacking between two adjacent side rails of 1D ladder chains.Such 2D sheets are further assembled via eight types of O—H…O hydrogen bonds to form a 3D supramolecular structure.According to topological viewpoint based on 1D chains,the 3D structure of 2 can also be deemed as the plywood-like array.In addition,2 shows strong ultraviolet fluorescence emission with an average life-time of 2.54 ns.CCDC:1865438,1;1865439,2.

关 键 词：Co(Ⅱ)配合物 Cd(Ⅱ)配合物 次级作用力 吡啶盐 荧光性质 

分 类 号：O614.812[理学—无机化学] O614.242[理学—化学]