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通过外源性手性中心嫁接策略对手性杂化金属卤化物进行自下而上的设计。

Bottom-Up Design of Chiral Hybrid Metal Halides via Exogenous Chiral-Center Graft Strategy.

作者信息

Ye Huang, Wang Peng, Wang Yifei, Guan Qianwen, Li Ruiqing, Zhang Chengshu, Li Hang, Li Lina, Zhu Zengkui, Wu Zhenyue, Luo Junhua

机构信息

State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China.

Fujian Science & Technology Innovation Laboratory for Optoelectric Information of China, Fuzhou, Fujian, 350108, P. R. China.

出版信息

Small. 2025 Jul;21(26):e2502275. doi: 10.1002/smll.202502275. Epub 2025 May 19.

Abstract

Chiral hybrid metal halides (CHMs) have emerged as promising platforms for developing spin-related condensed matter physics, owing to their inherent chirality and excellent semiconducting features. However, the current exploration for new CHMs is mainly restrained by the requirement of organic amines with inner chiral centers, which constrains the precise customization of organic parts and impedes their further development in subdivision fields of chiral science. Here, by applying an exogenous chirality graft strategy through the stereo retentive S2 reaction between homochiral epoxy chloropropane and achiral amines, a series of CHMs is successfully bottom-up designed. All the CHMs obtained from the strategy crystalize in the chiral space group and exhibit significant chiral characters including chiroptical activity and secondary harmonic generation. Additionally, the introduction of the exogenous chiral centers promotes the materials exhibit inherent chiral semiconductor features, which enables them to own the capability to intertangle with light with different states of helicity, provoking them potential in the application of circularly polarized light emission and detection. This work provides a new routine to design and synthesize CHMs conveniently and robustly, which may boost further investigation of chiral sciences.

摘要

手性杂化金属卤化物(CHMs)因其固有的手性和优异的半导体特性,已成为发展自旋相关凝聚态物理的有前景的平台。然而,目前对新型CHMs的探索主要受到具有内手性中心的有机胺的需求限制,这限制了有机部分的精确定制,并阻碍了它们在手性科学细分领域的进一步发展。在此,通过应用外源性手性嫁接策略,即通过同手性环氧氯丙烷与非手性胺之间的立体保留S2反应,成功地自下而上设计了一系列CHMs。从该策略获得的所有CHMs在手性空间群中结晶,并表现出显著的手性特征,包括手性光学活性和二次谐波产生。此外,外源性手性中心的引入促进了材料展现出固有的手性半导体特性,这使它们能够与不同螺旋状态的光相互纠缠,激发了它们在圆偏振光发射和检测应用中的潜力。这项工作提供了一种方便且稳健地设计和合成CHMs的新途径,这可能会推动对手性科学的进一步研究。

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