Versatile chiroptical induction/manipulation through specific solvation of ion pairs by alcohols

IF 10.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Science China Chemistry Pub Date : 2024-10-16 DOI:10.1007/s11426-024-2190-5

Chunhong Liu, Xin Chen, Yanling Shen, Ting Zhao, Dayang Zhou, Kun Li, Jiecheng Ji, Wanhua Wu, Xuemei Pu, Cheng Yang

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引用次数: 0

Abstract

While extensive research has explored manipulating supramolecular chirality through internal and external factors, the specific solvation effect remains uncharted territory. This study synthesized ortho-functionalized pillar[5]arene (P[5]) derivatives Mn and Dn via thiol-Michael addition, characterizing them through spectroscopic and X-ray single-crystal analyses. Mn and Dn interacted with chiral amines, yielding significant circular dichroism (CD) responses. Intriguingly, the chiral induction exhibited pronounced specific solvation effects, where achiral alcohols either enhanced, attenuated, or reversed CD signals. Testing over 40 alcohols revealed correlations between the specific solvation effects and alcohol polarity and acidity. Molecular dynamics simulations unveiled that the alcohol interacted distinctly through hydrogen bonding, with one ion pair bonding up to four alcohol molecules. The R_p- and S_p-preference of the P[5] core could be altered by the number of bonded alcohols. This work uncovers the critical role of alcohol-specific solvation in ion pair-involved chiral assembly, pertinent for asymmetric ion-pairing catalysis and the use of alcohol additives in organic solvents.

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来源期刊

Science China Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

7.30%

发文量

3787

审稿时长

2.2 months

期刊介绍： Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field. Categories of articles include: Highlights. Brief summaries and scholarly comments on recent research achievements in any field of chemistry. Perspectives. Concise reports on thelatest chemistry trends of interest to scientists worldwide, including discussions of research breakthroughs and interpretations of important science and funding policies. Reviews. In-depth summaries of representative results and achievements of the past 5–10 years in selected topics based on or closely related to the research expertise of the authors, providing a thorough assessment of the significance, current status, and future research directions of the field.