Li Ke, Xu Zhanqiang, Deng Han, Zhou Zhennan, Dang Yanfeng, Sun Zhe
Institute of Molecular Plus, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, 92 Weijin Road, Tianjin, 300072, China.
Beijing International Center for Mathematical Research, Peking University, Beijing, 100871, China.
Angew Chem Int Ed Engl. 2021 Mar 29;60(14):7649-7653. doi: 10.1002/anie.202016995. Epub 2021 Feb 26.
Dimeric cycloparaphenylene (CPP) architectures with well-defined flipping motion are constructed taking advantage of an efficient cyclocondensation reaction. Variable-temperature nuclear magnetic resonance (VT-NMR) analyses and theoretical calculations indicate rapid interconversion of cis and trans conformers at room temperature, while energetically favorable trans conformer exists at low temperature with the metastable cis conformer hidden. The trihexylsilylethynyl-substituted dimer exhibits bright emission in solution at 616 nm with quantum yield up to 80 %, representing the brightest CPP-based emitter beyond 600 nm. A 1:2 host-guest complex of the dimer and C is established with negative cooperativity, demonstrating the first example of 1:2 complex from CPP derivatives.
利用高效的环缩合反应构建了具有明确翻转运动的二聚体对亚苯基（CPP）结构。变温核磁共振（VT-NMR）分析和理论计算表明，顺式和反式构象异构体在室温下快速相互转化，而在低温下存在能量上更有利的反式构象异构体，亚稳的顺式构象异构体则隐藏其中。三己基硅乙炔基取代的二聚体在溶液中于616 nm处发出明亮的荧光，量子产率高达80%，是600 nm以上最亮的基于CPP的发光体。该二聚体与C形成了具有负协同性的1:2主客体复合物，这是CPP衍生物形成1:2复合物的首个例子。
