Han Xiao, Cheng Puxin, Yang Huanxin, Guan Junjie, Xin Mingyang, Li Geng, Li Xiyan, 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, P. R. China.
Science and Technology Institute of Advanced Technology, Furong Road 1, Wuhan, Hubei, 430050, P. R. China.
Angew Chem Int Ed Engl. 2025 Feb 10;64(7):e202419776. doi: 10.1002/anie.202419776. Epub 2025 Jan 2.
Chiral hybrid organic-inorganic metal halides (HOMHs) hold great promise in broad applications ranging from ferroelectrics, spintronics to nonlinear optics, owing to their broken inversion symmetry and tunable chiroptoelectronic properties. Typically, chiral HOMHs are constructed by chiral organic cations and metal anion polyhedra, with the latter regarded as optoelectronic active units. However, the primary design approaches are largely constrained to regulation of general components within structural formula. Herein, supramolecular approaches have been taken for the functionalization of chiral enantiomers by anchoring chiral cations with crown ether hosting molecules. Chiral HOMHs of R-/S-(18-crown-6@ClMBA)MnBr have been thus obtained with boosted linear and nonlinear chiroptical properties. The self-assembled cations lead to enhanced structural rigidity, which promote near-unity green light emission and strong circularly polarized luminescence with a high asymmetry factor, along with high efficiency second-order nonlinear optical responses. In particular, these chiral HOMH single crystals demonstrate a sensitive discrimination for circularly polarized laser in the near-infrared region with the nonlinear optical asymmetry factor (g) as high as 1.8. This work highlights the contribution of supramolecular assembly in improving chiroptical performances, offering valuable insights for the design of new chiral HOMH materials with promising application potentials as linear and nonlinear CPL emitters and detectors.
手性有机-无机杂化金属卤化物（HOMHs）因其具有破缺的反演对称性和可调谐的手性光电子特性，在从铁电体、自旋电子学到非线性光学等广泛应用中具有巨大潜力。通常，手性HOMHs由手性有机阳离子和金属阴离子多面体构成，后者被视为光电子活性单元。然而，主要的设计方法在很大程度上局限于对结构式中一般组分的调控。在此，通过将手性阳离子与冠醚主体分子锚定，采用超分子方法对手性对映体进行功能化。由此获得了具有增强的线性和非线性手性光学性质的R-/S-(18-冠-6@ClMBA)MnBr手性HOMHs。自组装阳离子导致结构刚性增强，促进了接近单位的绿色发光和具有高不对称因子的强圆偏振发光，以及高效的二阶非线性光学响应。特别是，这些手性HOMH单晶在近红外区域对圆偏振激光表现出灵敏的辨别能力，其非线性光学不对称因子（g）高达1.8。这项工作突出了超分子组装在改善手性光学性能方面的贡献，为设计具有作为线性和非线性圆偏振发光体及探测器的有前景应用潜力的新手性HOMH材料提供了有价值的见解。
