鉑(II)鑷子誘導具有優良環境耐受性的超分子手性產生

鉑（II）鑷子誘導具有優良環境耐受性的超分子手性產生

作者：

小柯機器人

發布時間：2020/11/2 16:53:22

中國科學技術大學高分子科學與工程系Feng Wang小組的最新研究揭示了鉑(II)引起的超分子Chirogenesis鑷子的環境耐受性。 相關論文於2020年10月29日發表在《德國應用化學》雜誌上。

據介紹，超分子手性產生（chirogenesis）已成為一種在人工系統中打破對稱性的有效的策略。然而，手性產生源信號對環境變化具有高度的敏感性，這對於它們在不對稱催化，手性光器件中的應用是不利的。

研究人員開發了一種有效的策略來解決這個問題，即構造非共價作用的鑷子/客體複合物（tweer/guest complexes），該複合物通過兩倍的供體-受體和Pt (II)- Pt(II) 金屬相互作用而穩定。客體封裝後，非手性Pt（II）鑷子上的兩個鉗子經歷立體有擇的扭曲，以最大程度地減少空間排斥，從而將鑷子/客體複合物鎖定為優選的手性構象。誘導的手性光效應顯示優秀的溶劑和溫度耐受性，歸因於強的鑷子/客體結合力；該結合力是通過靜電和所涉及非共價相互作用的去溶劑化效應之間的平衡產生。

此外，鑷子/客體複合物的分層和多組分超分子組裝提供了一種方便的方法來調製強度的手性信號。總的來說，當前的研究為具有優異環境耐受性的人工超分子手性產生開闢了道路。

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