Redox‐Triggered Chirality Switching and Guest‐Capture/Release with a Pillar[6]arene‐Based Molecular Universal Joint
Chao Xiao, Wanhua Wu, Wenting Liang, Da‐Yang Zhou, Kuppusamy Kanagaraj, Guo Cheng, Dan Su, Zhihui Zhong, Jason J. Chruma, Cheng Yang
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.