中国科学技术大学高分子科学与工程系Feng Wang小组的最新研究揭示了铂(II)引起的超分子Chirogenesis镊子的环境耐受性。 相关论文于2020年10月29日发表在《德国应用化学》杂志上。

据介绍，超分子手性产生（chirogenesis）已成为一种在人工系统中打破对称性的有效的策略。然而，手性产生源信号对环境变化具有高度的敏感性，这对于它们在不对称催化，手性光器件中的应用是不利的。

研究人员开发了一种有效的策略来解决这个问题，即构造非共价作用的镊子/客体复合物（tweer/guest complexes），该复合物通过两倍的供体-受体和Pt (II)- Pt(II) 金属相互作用而稳定。客体封装后，非手性Pt（II）镊子上的两个钳子经历立体有择的扭曲，以最大程度地减少空间排斥，从而将镊子/客体复合物锁定为优选的手性构象。诱导的手性光效应显示优秀的溶剂和温度耐受性，归因于强的镊子/客体结合力；该结合力是通过静电和所涉及非共价相互作用的去溶剂化效应之间的平衡产生。

此外，镊子/客体复合物的分层和多组分超分子组装提供了一种方便的方法来调制强度的手性信号。总的来说，当前的研究为具有优异环境耐受性的人工超分子手性产生开辟了道路。

附：英文原文

Title: Supramolecular Chirogenesis Induced by Platinum(II) Tweezers with Excellent Environmental Tolerance

Author: Mingyang Liu, Yifei Han, Hua Zhong, Xiaolong Zhang, Feng Wang

Issue&Volume:

Abstract: Supramolecular chirogenesis has emerged as an effective strategy to access symmetry breaking in artificial systems. However, the chirogenic signals suffer from high susceptibility toward environmental variations, which are disadvantageous for their applications in asymmetric catalysis, chiroptical devices etc. Herein an effective strategy has been developed to address this issue, by constructing non‐covalent tweezer/guest complexes stabilized by two‐fold donor–acceptor and Pt(II)‐‐‐Pt(II) metal–metal interactions. Upon guest encapsulation, the two pincers on achiral Pt(II) tweezer undergo stereospecific twist to minimize steric repulsion, thus locking the tweezer/guest complexes into preferred chiral conformations. The induced chiroptical effects display outstanding solvent‐ and temperature‐ tolerance, ascribed to strong tweezer/guest binding strength via the balance between electrostatic and desolvation effects for the involved non‐covalent interactions. Moreover, hierarchical and multi‐component supramolecular assembly of tweezer/guest complexes provide a convenient way to modulate chirogeneic signals for their intensities. Overall, the current study opens up new avenues toward artificial supramolecular chirogenesis with excellent environmental tolerability.

DOI: 10.1002/anie.202012901

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202012901