Redox-Triggered Chirality Switching and Guest-Capture/Release with a Pillar[6]arene-Based Molecular Universal Joint

Chao Xiao; Wanhua Wu; Wenting Liang; Dayang Zhou; Kuppusamy Kanagaraj; Guo Cheng; Dan Su; Zhihui Zhong; Jason J Chruma; Cheng Yang

doi:10.1002/anie.201916285

Redox-Triggered Chirality Switching and Guest-Capture/Release with a Pillar[6]arene-Based Molecular Universal Joint

Angew Chem Int Ed Engl. 2020 May 18;59(21):8094-8098. doi: 10.1002/anie.201916285. Epub 2020 Mar 3.

Authors

Affiliations

¹ Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, State Key Laboratory of Biotherapy, and Healthy Food Evaluation Research Center, Sichuan University, Chengdu, 610064, China.
² Institute of Environmental Sciences, Shanxi University, China.
³ Comprehensive Analysis Center, ISIR, Osaka University, Japan.

PMID: 31958199
DOI: 10.1002/anie.201916285

Abstract

A chiral electrochemically responsive molecular universal joint (EMUJ) was synthesized by fusing a macrocyclic pillar[6]arene (P[6]) to a ferrocene-based side ring. A single crystal of an enantiopure EMUJ was successfully obtained, which allowed, for the first time, the definitive correlation between the absolute configuration and the circular dichroism spectrum of a P[6] derivative to be determined. The self-inclusion and self-exclusion conformational change of the EMUJ led to a chiroptical inversion of the P[6] moiety, which could be manipulated by both solvents and changes in temperature. The EMUJ also displayed a unique redox-triggered reversible in/out conformational switching, corresponding to an occupation/voidance switching of the P[6] cavity, respectively. This phenomenon is an unprecedented electrochemical manipulation of the capture and release of guest molecules by supramolecular hosts.

Keywords: chirality inversion; electrochemistry; molecular universal joint; pillar[6]arene; supramolecular chemistry.

Abstract

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