| 乳酸类合成子构建的四连接螺旋手性配位聚合物的合成、结构和光催化性质 | |
| Four-connected helical chiral coordination polymers based on lactate synthons: Syntheses, structures, and photo-catalytic properties | |
| 摘要: 通过乳酸衍生物和3-溴-4-羟基苯甲酸的组合得到对映体3-溴-4-(((1R)-1-羧基乙基)氧基)苯甲酸(R-H2bba)和3-溴-4-(((1S)-1-羧基乙基)氧基)苯甲酸(S-H2bba)。以其为手性合成子在水热条件下分别与1，3-二(吡啶-4-基)丙烷(1，3-dpp)和Ni2+反应，构建了对映手性配位聚合物{[Ni (R-bba)(1，3-dpp)(H2O)0.5]·1.5H2O}n (HU12-R)和{[Ni (S-bba)(1，3-dpp)(H2O)0.5]·1.5H2O}n (HU12-S)。结构分析揭示HU12-R和HU12-S是具有dia网络特征的三维螺旋骨架。在骨架中，阴离子配体R-bba2-和S-bba2-分别与Ni2+中心连接在一起围绕21螺旋轴得到一对小的对映螺旋链，而1，3-dpp与Ni2+中心则围绕41螺旋轴构建出另外一对大的对映螺旋链。电化学测试显示HU12-R属n型半导体，具有低阻抗性质，对紫外可见光有很强的吸收能力。进一步光催化实验证实在紫外光照射下所得配合物对染料降解有明显催化效果。 | |
| 关键词: 手性配合物 乳酸合成子 dia型网络 螺旋结构 光催化活性 | |
| 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.ZK2022576)资助。 | |
| Abstract: Enantiomeric lactic derivatives and 3-bromo-4-hydroxybenzoate were used as starting materials to obtain a pair of enantiomers 3-bromo-4-(((1R)-1-carboxyethyl)oxy)benzoic acid (R-H2bba) and 3-bromo-4-(((1S)-1-carboxy-ethyl)oxy)benzoic acid (S-H2bba). As new synthons, R-H2bba and S-H2bba can provide variable coordination modes by two carboxylate groups and chiral source by lactate unit. In the presence of 1,3-di(pyridine-4-yl)propane (1,3-dpp), R-H2bba and S-H2bba further assembled with Ni2+ ions under the hydrothermal condition to obtain a pair of chiral coordination polymers (CCPs) {[Ni(R-bba)(1,3-dpp)(H2O)0.5]·1.5H2O}n (HU12-R) and {[Ni(S-bba) (1,3-dpp) (H2O)0.5]·1.5H2O}n (HU12-S), respectively. Structural analysis revealed complexes HU12-R and HU12-S are 3D helical frameworks with 4-connected dia net. In complexes HU12-R and HU12-S, R-bba2- and S-bba2- anions are respectively connected by Ni2+ centers to form a pair of small enantiomeric helical chains around 21 screw axis. In contrast, 1,3-dpp ligands and Ni2+ centers construct another pair of large enantiomeric helical chains around 41 or 43 screw axis, respectively. Moreover, the results of electrochemical testing indicated that complex HU12-R is an n-type semiconductor and has a strong absorbing ability for UV-Vis light and low resistance in charge transportation. By comparing with R-H2bba, 1,3-dpp, and Ni2+ ions, HU12-R indicates obvious catalytic activity in the degradation of dyes under ultraviolet light. | |
| Keywords: chiral complex lactate synthon dia net helical structure photo-catalytic activity | |
| 投稿时间：2023-07-12 修订日期：2023-11-14 | |
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| 徐中轩,吴俊,张远婷,武梦杰.乳酸类合成子构建的四连接螺旋手性配位聚合物的合成、结构和光催化性质[J].无机化学学报,2024,40(2):336-344. | |
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