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

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

机构地区：[1]Key Laboratory of Green Chemistry&Technology of Ministry of Education,Sichuan University,Chengdu 610064,China [2]Comprehensive Analysis Center,ISIR,Osaka University,Osaka 565-0871,Japan

出　　处：《Science China Chemistry》2025年第2期610-621,共12页中国科学(化学英文版)

基　　金：supported by the National Natural Science Foundation of China(22471182,22271201,92056116,22422108,22171194,22201194);the Fundamental Research Funds for the Central Universities(20826041D4117).

摘　　要：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 Rp-and Sp-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.

关 键 词：chiroptical induction specific solvation ion pair arene H-BOND 

分 类 号：TQ413[化学工程]