Xin Mingyang, Cheng Puxin, Shi Rongchao, Guan Junjie, Han Xiao, Wang Zhihua, Li Quanwen, Li Geng, Zheng Yongshen, Xu Jialiang, Bu Xian-He
School of Materials Science and Engineering, Tianjin Key Laboratory of Metal and Molecular Materials Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tongyan Road 38, Tianjin 300350, PR China.
Key Laboratory of Rare Earths, Chinese Academy of Sciences, China Rare Earth Group Research Institute, Ganzhou, Jiangxi 341000, PR China.
J Am Chem Soc. 2024 Sep 25;146(38):26534-26542. doi: 10.1021/jacs.4c10507. Epub 2024 Sep 10.
Dynamic twisting crystals, combining the features of dynamic crystals and twisting crystals, promise advanced applications in targeted drug delivery, biosensors, microrobots, and spiral optoelectronics. However, the determination of dynamic twisting crystals with specific directions remains a formidable challenge in practical applications. Herein, based on organic-inorganic hybrid metal halide (OIHMH) single crystals, we have realized the chirality-induced macroscopic twisting of single crystals driven by a thermo-induced topochemical dehydration reaction. These crystals exhibit molecular-chirality-induced twisting upon heating, along with reversals in their linear chiroptical circular dichroism and nonlinear chiroptical second harmonic generation circular dichroism. Such an induced twisting has been attributed to the alteration of the helical arrangement of chiral cation post-topochemical dehydration. The feasibility of tuning the macroscopic twisting of OIHMH single crystals and the switching in their linear and nonlinear chiroptical properties might open up new avenues for developing dynamic crystals for microactuating and optoelectronic applications.
动态扭曲晶体结合了动态晶体和扭曲晶体的特性，有望在靶向药物递送、生物传感器、微型机器人和螺旋光电子学等领域得到先进应用。然而，在实际应用中，确定具有特定方向的动态扭曲晶体仍然是一项艰巨的挑战。在此，基于有机-无机杂化金属卤化物（OIHMH）单晶，我们通过热诱导拓扑化学脱水反应实现了手性诱导的单晶宏观扭曲。这些晶体在加热时表现出手性诱导的扭曲，同时其线性手性光学圆二色性和非线性手性光学二次谐波产生圆二色性发生反转。这种诱导扭曲归因于拓扑化学脱水后手性阳离子螺旋排列的改变。调节OIHMH单晶宏观扭曲以及其线性和非线性手性光学性质切换的可行性，可能为开发用于微驱动和光电子应用的动态晶体开辟新途径。
