α-Cyclodextrin-Catalyzed Symmetry Breaking and Precise Regulation of Supramolecular Self-Assembly Handedness with Harata-Kodaka's Rule.
α-Cyclodextrin-Catalyzed Symmetry Breaking and Precise Regulation of Supramolecular Self-Assembly Handedness with Harata-Kodaka's Rule.
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DOI：
10.1021/acsnano.1c06766
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发表时间：
2021-10
期刊：
影响因子：
17.1
通讯作者：
Wanwan Zhi;Zhichen Pu;Cheng Ma;Kaerdun Liu;Xuejiao Wang;Jianbin Huang;Yunlong Xiao;Yun Yan
中科院分区：
文献类型：
--
作者：
Wanwan Zhi;Zhichen Pu;Cheng Ma;Kaerdun Liu;Xuejiao Wang;Jianbin Huang;Yunlong Xiao;Yun Yan
在20世纪70 - 90年代已经发现了预测由环糊精诱导的客体分子的手性的Harata-Kodaka规则，但是其控制自组装结构的超分子手性的能力尚未得到充分的认识。在这里，我们表明，在一个协调的自组装系统，能够形成外消旋锥壳对称性破缺发生，如果配体是预线程到α-环糊精之前，金属离子的添加，和锥壳的手性可以合理地操纵通过创建两个场景的Harata-Kadaka规则，通过控制主客体动力学。由于配合物具有较强的自组装能力，配体会从α-环糊精的空腔中脱出，但会将诱导的手性留给配位自组装，从而催化对称性破缺。研究结果表明，在超分子水平上，浓度和摩尔比等动力学因素对对称性破缺有重要影响。目前的策略提供了一个很有前途的方法，对称性破缺和操纵手性的自组装材料形成的非手性分子。
Harata-Kodaka's rule predicting the induced chirality of the guest molecules by cyclodextrins has been discovered in the 1970-1990s, yet its ability to control the supramolecular handedness of self-assembled structures has not been sufficiently recognized. Here we show that in a coordinating self-assembly system that is able to form racemic cone shells symmetry breaking occurs if the ligand is prethreaded into α-cyclodextrin prior to metal ion addition, and the handedness of cone shells can be rationally manipulated by creating the two scenarios of the Harata-Kadaka rule through controlling the host-guest dynamics. Since the coordination complexes have strong self-assembling ability, the coordinating ligand would dethread from the cavity of α-cyclodextrin but leaving the induced chirality to the coordinating self-assembly, thus catalyzing symmetry breaking. This work reveals that the dynamic factors such as concentration and molar ratio may play important roles in symmetry breaking at the supramolecular level. The current strategy provides a promising method for the symmetry breaking and manipulation of the handedness of self-assembled materials formed by achiral molecules.