刚性配体经自发拆分构筑的dia型螺旋对映框架
Enantiomeric Helical Frameworks with dia Net Based on Rigid Ligands from Spontaneous Resolution
作者单位E-mail
徐中轩 遵义师范学院化学化工学院, 遵义 563002 xuzhongxuan4201@163.com 
李立凤 遵义师范学院化学化工学院, 遵义 563002  
白旭玲 遵义师范学院化学化工学院, 遵义 563002  
徐仕菲 遵义师范学院化学化工学院, 遵义 563002  
摘要: 刚性的2-甲氧基对苯二甲酸(H2MPA)和2,5-二(1H-咪唑-1-基)吡啶(2,5-DIP)与Zn2+通过自发拆分得到了一对组成为[Zn(MPA)(2,5-DIP)]·1.4H2O的对映体。结构分析揭示分别结晶于手性空间群P41P43,Flack参数都接近于0。在中,Zn2+与配体MPA2-和/或2,5-DIP沿着c轴方向形成了3对对映的螺旋链。尽管3种螺旋链的组成和结构不同,但中的螺旋链都表现为右手构型,而中的螺旋链则呈对映的左手构型。此外,由3种螺旋链构建的孔道宽度分别达到了1.1 nm×1.1 nm、1.1 nm×0.8 nm和0.8 nm×0.8 nm,如此空旷的结构导致整个框架是五重穿插特征的dia型网络。此外,配合物1在紫外可见光谱的紫外区有强的吸收,而固体荧光测试表明其有蓝色荧光特征,强的荧光发射峰在435 nm处。
关键词: 手性配位聚合物  自发拆分  螺旋链  五重穿插结构  dia网络
基金项目: 国家自然科学基金(No.21761036)和贵州省自然科学基金(No.20181181)资助。
Abstract: The enantiomers of complex 1 ( and ), [Zn(MPA)(2,5-DIP)]·1.4H2O (H2MPA=2-methoxyterephthalic acid, 2,5-DIP=2,5-di(1H-imidazol-1-yl)pyridine) were obtained by spontaneous resolution upon crystallization in the absence of any enantiopure reagents under hydrothermal condition. X-ray crystallography reveals that complexes and crystallize in chiral space groups P41 and P43 with near-zero Flack parameters, respectively. In complexes and , three types of helical chains are constructed by Zn2+ ions, MPA2- and/or 2,5-DIP ligands along c axis. Although these helical chains contain different components and show different structures, they still have same righthanded helical configuration in and left-handed helical configuration in , respectively. For the width of channels based on helical chains are up to 1.1 nm×1.1 nm, 1.1 nm×0.8 nm and 0.8 nm×0.8 nm, respectively, and such empty structures result in 5-fold-interpenetrating 3D frameworks with 4-connected dia net in complexes and . Furthermore, UV-Vis spectra measurement for 1 showed a strong absorption band in ultraviolet region, while solid fluorescence curve revealed blue fluorescence property with emission peak at about 435 nm in complex 1.
Keywords: chiral coordination polymers  spontaneous resolution  helical chain  5-fold-interpenetrating structure  dia net
投稿时间:2020-12-13 修订日期:2021-04-18
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徐中轩,李立凤,白旭玲,徐仕菲.刚性配体经自发拆分构筑的dia型螺旋对映框架[J].无机化学学报,2021,37(7):1191-1196.
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