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聚集诱导发光晶体中的分子运动:力致原纤维滑动实现光致发光开启。

Molecular Motions in AIEgen Crystals: Turning on Photoluminescence by Force-Induced Filament Sliding.

机构信息

Department of Chemistry, Hong Kong Branch of Chinese National Engineering, Research Center for Tissue Restoration and Reconstruction, Institute for Advanced Study, Department of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.

HKUST-Shenzhen Research Institute, No. 9 Yuexing first RD, South Area, Hi-tech Park, Nanshan, Shenzhen 518057, China.

出版信息

J Am Chem Soc. 2020 Aug 26;142(34):14608-14618. doi: 10.1021/jacs.0c06305. Epub 2020 Aug 4.

Abstract

Life process is amazing, and it proceeds against the eternal law of entropy increase through molecular motion and takes energy from the environment to build high-order complexity from chaos to achieve evolution with more sophisticated architectures. Inspired from the elegance of life process and also to effectively exploit the undeveloped solid-state molecular motion, two unique chiral Au(I) complexes were elaborately developed in this study, in which their powders could realize a dramatic transformation from nonemissive isolated crystallites to emissive well-defined microcrystals under the stimulation of mechanical force. Such an unusual crystallization was presumed to be caused by molecular motions driven by the formation of strong aurophilic interactions as well as multiple C-H···F and π-π interactions. Such a prominent macroscopic off/on luminescent switching could also be achieved through extremely subtle molecular motions in the crystal state and presented a filament sliding that occurred in a layer-by-layer molecular stacking fashion with no involvement of any crystal phase transition. Additionally, it had been demonstrated that the manipulation of the solid-state molecular motions could result in the generation of circularly polarized luminescence.

摘要

生命过程令人惊叹,它通过分子运动逆着熵增的永恒法则进行,并从环境中获取能量,从而从混沌中构建更高阶的复杂性,实现更复杂结构的进化。受生命过程的优雅启发,同时为了有效利用尚未开发的固态分子运动,本研究精心设计了两种独特的手性 Au(I) 配合物,其粉末在机械力的刺激下可以实现从非发光孤立晶体到发光的明确定型微晶体的剧烈转变。这种不寻常的结晶被认为是由强金键相互作用以及多种 C-H···F 和 π-π 相互作用驱动的分子运动引起的。这种显著的宏观开/关发光开关也可以通过晶体状态下极其微妙的分子运动来实现,并呈现出一种以层叠方式发生的丝状滑动,而不涉及任何晶体相变。此外,已经证明,固态分子运动的操控可以产生圆偏振发光。

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