State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210023, China.
National Laboratory of Solid State Microstructures and Department of Physics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210093, China.
Nat Commun. 2017 Dec 14;8(1):2131. doi: 10.1038/s41467-017-02260-2.
Chiral expression from the molecular to macroscopic level is common in biological systems, but is difficult to realise for coordination polymers (CPs). The assembly of homochiral CPs in both crystalline and helical forms can provide a bridge for understanding the relationship between the molecular and macroscopic scales of chirality. Herein, we report homochiral helices of [Tb(R- or S-pempH)]∙2HO (R - or S -1) (pempH = (1-phenylethylamino)methylphosphonic acid) and their crystalline counterparts (R - or S -3), which are formed at different pH of the reaction mixtures under hydrothermal conditions. By combining the experiments and molecular simulations, we propose that the formation of helices of R -1 or S -1 occurs via a hierarchical self-assembly route, which involves twisted packing due to the geometric incompatibility of the different types of chains. The observed chiral transcription from molecules to morphologies is significant for understanding bio-related self-assembly processes on the nano- to macro-scale.
手性从分子到宏观水平的表达在生物系统中很常见，但在配位聚合物 (CPs) 中很难实现。手性同型 CPs 的组装以晶体和螺旋形式存在，可以为理解分子和宏观手性尺度之间的关系提供桥梁。在此，我们报告了[Tb(R-或 S-pempH)]∙2HO (R-或 S-1) (pempH = (1-苯乙氨基)甲基膦酸)的手性螺旋及其晶体对应物 (R-或 S-3)，它们是在水热条件下不同 pH 的反应混合物中形成的。通过结合实验和分子模拟，我们提出 R-1 或 S-1 的螺旋形成是通过一个分级自组装途径发生的，该途径涉及由于不同类型链的几何不兼容性而导致的扭曲堆积。从分子到手性形态的观察到的转录对于理解纳米到宏观尺度上与生物相关的自组装过程具有重要意义。
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