Redox‐Triggered Chirality Switching and Guest‐Capture/Release with a Pillar [6] arene‐Based Molecular Universal Joint
Redox‐Triggered Chirality Switching and Guest‐Capture/Release with a Pillar [6] arene‐Based Molecular Universal Joint
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氧化还原 — 触发手性切换和客体 — 使用支柱 [6] 芳烃 — 分子万向节捕获/释放
DOI：
10.1002/ange.201916285
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发表时间：
2020
期刊：
影响因子：
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通讯作者：
Cheng Yang
中科院分区：
文献类型：
--
作者：
Chao Xiao;Wanhua Wu;Wenting Liang;Dayang Zhou;Kuppusamy Kanagara;Guo Cheng;Dan Su;Zhihui Zhong;Jason Joseph Chruma;Cheng Yang
将大环柱[6]芳烃(P[6])融合到二茂铁基侧环上，合成了手性电化学响应型分子万向节(EMUJ)。成功地获得了对映体EMUJ的单晶，首次确定了P[6]衍生物的绝对构型与圆二色谱之间的明确关联。EMUJ的自包含和自排除构象变化导致了P[6]部分的手性反转，这可以被溶剂和温度的变化所操纵。EMUJ还表现出独特的氧化还原触发的可逆In/Out构象转换，分别对应于P[6]空穴的占据/空穴转换。这一现象是超分子宿主对客体分子捕获和释放的一种前所未有的电化学操纵。
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.