Chen Gaoyu, Zhou Kunhong, Liu Qingda, Liu Junli, Xu Xiangxing, Shi Wenxiong, Jiang Jinzhou, Zhang Xinwen, Dong Lizhu, Xie Linghai, Zhang Xiaoyu, Zhang Niuniu, Xu Dongdong, Bao Jianchun, Wang Xun
Jiangsu Key Laboratory of New Power Batteries, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, P. R. China.
Frontiers Science Center for Flexible Electronics, Institute of Flexible Electronics (IFE), Northwestern Polytechnical University, Xi'an 710072, China.
J Am Chem Soc. 2025 Apr 9;147(14):12347-12359. doi: 10.1021/jacs.5c04134. Epub 2025 Mar 26.
The phenomenon of chiral symmetry breaking during the crystallization of achiral molecules or ions, which leads to the formation of controllable enantiomerically pure crystals, has garnered significant interest but remains a challenge to fully overcome. This presents a particularly formidable obstacle in the creation of three-dimensional (3D) structured chiral all-inorganic perovskites, further complicated by their achiral crystalline space groups. In this report, we successfully synthesized right- or left-handed (P/M) chiral 3D P/M-CsPbX (X = Cl, Cl-Br, Br, Br-I) perovskite subnanowires (SNWs), in which Pb(II) can be partially substituted by hetero ions, such as Cu(II), Sn(II), and Mn(II). The selective control of the SNW handedness was achieved through the strategic incorporation of trace chiral amine enantiomers. The chiroptical activity arises from the helical structure of the SNWs. The mechanisms underlying the formation of this chiral structure were systematically investigated and interpreted by using a thermodynamic model. We utilized the chiral P/M-CsPbBr SNWs to fabricate circularly polarized light (CPL) photodetectors, which exhibited an impressive photocurrent dissymmetry factor () of 0.75. In the field of spin light-emitting diodes (spin-LEDs), circularly polarized electroluminescence (CPEL) was accomplished by employing the SNWs as a dual-functional material that provides both chiral-induced spin selectivity (CISS) and CPL emission capabilities.
在非手性分子或离子结晶过程中出现的手性对称性破缺现象，可导致形成可控的对映体纯晶体，这一现象已引起广泛关注，但要完全克服仍具挑战。这在创建三维（3D）结构的手性全无机钙钛矿时构成了特别巨大的障碍，其非手性晶体空间群进一步加剧了复杂性。在本报告中，我们成功合成了右手或左手（P/M）手性3D P/M-CsPbX（X = Cl、Cl-Br、Br、Br-I）钙钛矿亚纳米线（SNW），其中Pb（II）可被诸如Cu（II）、Sn（II）和Mn（II）等杂离子部分取代。通过策略性引入痕量手性胺对映体实现了对SNW手性的选择性控制。旋光活性源于SNW的螺旋结构。利用热力学模型系统研究并解释了这种手性结构形成的机制。我们利用手性P/M-CsPbBr SNW制造了圆偏振光（CPL）光电探测器，其表现出令人印象深刻的光电流不对称因子（）为0.75。在自旋发光二极管（spin-LED）领域，通过将SNW用作兼具手性诱导自旋选择性（CISS）和CPL发射能力的双功能材料，实现了圆偏振电致发光（CPEL）。
