| 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 |
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| 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1Δ和1Λ。结构分析揭示1Δ和1Λ分别结晶于手性空间群P41和P43，Flack参数都接近于0。在1Δ和1Λ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1Δ中的螺旋链都表现为右手构型，而1Λ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 (1Δ and 1Λ), [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 1Δ and 1Λ crystallize in chiral space groups P41 and P43 with near-zero Flack parameters, respectively. In complexes 1Δ and 1Λ, 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 1Δ and left-handed helical configuration in 1Λ, 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 1Δ and 1Λ. 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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