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
作者单位E-mail
任永合 山东科技大学化学与生物工程学院, 青岛 266590  
李鲁超 山东科技大学化学与生物工程学院, 青岛 266590  
丁琦晖 山东科技大学化学与生物工程学院, 青岛 266590  
黄永清 山东科技大学化学与生物工程学院, 青岛 266590 yqhuangskd@163.com 
赵越 南京大学化学化工学院, 配位化学国家重点实验室, 南京 210023  
摘要: 以3-羧基-1-(4-羧基苄基)吡啶溴酸盐((H2L) Br)分别与Co (Ⅱ)和Cd (Ⅱ)金属盐反应,制备了2个配合物[Co (L)2(H2O)4]·2H2O (1)和[Cd (L)2(H2O)]·3H2O (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(H2O)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。
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
基金项目: 国家自然科学基金(No.21201111)资助。
Abstract: Two complexes with chemical formulas[Co(L)2(H2O)4]·2H2O (1) and[Cd(L)2(H2O)]·3H2O (2) were obtained by the reaction of 3-carboxy-1-(4-carboxybenzyl)-pyridinium bromide ((H2L) 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 and π-π interaction components and can be used as supramolecular synthons. In the case of 1, mononuclear[Co(L)2(H2O)4] coordination entities are first joined via hydrogen bonding to produce channel-structured 2D layers, which are further stacked via π-π stacking effect in an interdigitating fashion, generating a 3D porous supramolecular assembly. 2 features a polymeric 1D zigzag chain structure, which is connected via π-π interactions 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 of π-π stacking 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.
Keywords: Co(Ⅱ) complex  Cd(Ⅱ) complex  secondary interaction  pyridinium  luminescence property
投稿时间:2020-12-27 修订日期:2021-09-07
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任永合,李鲁超,丁琦晖,黄永清,赵越.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[J].无机化学学报,2021,37(11):2047-2058.
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