Supramolecular Assembly Enhanced Linear and Nonlinear Chiroptical Properties of Chiral Manganese Halides
Xiao Han, Puxin Cheng, Huanxin Yang, Junjie Guan, Mingyang Xin, Geng Li, Xiyan Li, Yongshen Zheng, Yongshen Zheng, Jialiang Xu, Xian‐He Bu
Abstract
Abstract 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) 2 MnBr 4 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 SHG‐CD ) 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.