Manipulating stereo-communication in binaphthol-bridged - and -cyclodextrins to develop -selective chiroptical pH switching and anion sensing in water

IF 4.7 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Chemistry Frontiers Pub Date : 2025-08-16 DOI:10.1039/d5qo00910c

Giovanni Preda, Sonia La Cognata, Laura Pedraza, Laurine Carlier, Maxime Kolb, Gennaro Pescitelli, Valeria Amendola, Dominique Armspach, Dario Pasini

{"title":"Manipulating stereo-communication in binaphthol-bridged - and -cyclodextrins to develop -selective chiroptical pH switching and anion sensing in water","authors":"Giovanni Preda, Sonia La Cognata, Laura Pedraza, Laurine Carlier, Maxime Kolb, Gennaro Pescitelli, Valeria Amendola, Dominique Armspach, Dario Pasini","doi":"10.1039/d5qo00910c","DOIUrl":null,"url":null,"abstract":"Molecular structures comprising naturally-occurring, stereodefined cyclodextrins and binaphthyls as bridging units have been realized, designed in such a way that the stereocommunication mode between the two chiral entities is unfavourable ('chiral mismatch'). The induced strain translates into highly responsive chiroptical behavior. On one side, the binaphthol-containing structure functions as a pH-controlled, single-molecule chiroptical switch, with reversal of the optical activity from acidic to basic conditions in a fully reversible manner. Additionally, the same host molecule demonstrates a pronounced chiroptical response to perrhenate in aqueous solution at pH 2.5, showing excellent selectivity for this specific anion. Computational analysis confirmed that the major effect of ReO4– complexation is making new conformations accessible to the binaphthol moiety with a large variation of the associated dihedral angles.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"70 1","pages":""},"PeriodicalIF":4.7000,"publicationDate":"2025-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5qo00910c","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}

引用次数: 0

Abstract

Molecular structures comprising naturally-occurring, stereodefined cyclodextrins and binaphthyls as bridging units have been realized, designed in such a way that the stereocommunication mode between the two chiral entities is unfavourable ('chiral mismatch'). The induced strain translates into highly responsive chiroptical behavior. On one side, the binaphthol-containing structure functions as a pH-controlled, single-molecule chiroptical switch, with reversal of the optical activity from acidic to basic conditions in a fully reversible manner. Additionally, the same host molecule demonstrates a pronounced chiroptical response to perrhenate in aqueous solution at pH 2.5, showing excellent selectivity for this specific anion. Computational analysis confirmed that the major effect of ReO₄^– complexation is making new conformations accessible to the binaphthol moiety with a large variation of the associated dihedral angles.

查看原文本刊更多论文

操纵联萘酚桥接-和-环糊精中的立体通信，以开发水中-选择性的热带pH开关和阴离子传感

由天然存在的、立体定义的环糊精和双萘基作为桥接单元的分子结构已经实现，其设计方式不利于两种手性实体之间的立体通信模式（“手性不匹配”）。诱导的应变转化为高度敏感的热带行为。一方面，含双萘酚的结构作为ph控制的单分子光学开关，以完全可逆的方式将光学活性从酸性条件逆转到碱性条件。此外，同样的宿主分子在pH为2.5的水溶液中对过透酸盐表现出明显的热性反应，对这种特定阴离子表现出极好的选择性。计算分析证实，ReO4 -络合的主要作用是使联萘酚部分产生新的构象，而相关的二面角变化很大。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Organic Chemistry Frontiers CHEMISTRY, ORGANIC-

CiteScore

7.90

自引率

11.10%

发文量

686

审稿时长

1 months

期刊介绍： Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.