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Hybrid organic−inorganic metal halides (HOMHs) have emerged as an ideal platform for the construction of semiconductor materials with promising optoelectronic properties. A number of HOMHs based on different metals including Sb3+ have been demonstrated with second‐harmonic generation (SHG) properties, but their nonlinear optical (NLO) performances including effective conversion wavelength range, optical stability, and NLO coefficients are not yet satisfactory. Here, by adopting a molecular design involving fluorine‐substitution on the achiral organic ammonium, this work has synthesized single crystals of two new chiral noncentrosymmetric HOMHs, (2‐FPEA)2SbX5 (X = Cl and Br), with large polarization ratios and outstanding optical transparency. The second‐order NLO coefficients of (2‐FPEA)2SbCl5 and (2‐FPEA)2SbBr5 are determined to be ≈24.3 and 21.6 pm V−1. Significantly, the Sb3+‐based HOMHs enable very high thermal stability and laser resistance. The distinguished laser‐induced damage thresholds (LDTs) have been estimated to be as high as 3.44 mJ cm−2 for (2‐FPEA)2SbCl5 and 3.32 mJ cm−2 for (2‐FPEA)2SbBr5, higher than that of the reported HOMHs. Such a highly efficient SHG performance and stability indicate the promising future of these Sb3+‐based metal halides for nonlinear photonic applications. [ABSTRACT FROM AUTHOR]

Chiral hybrid perovskites have shown great potential for applications in next‐generation optoelectronic devices. The intrinsic asymmetric structures of these chiral hybrid perovskites make them particularly promising for second‐order nonlinear optics (NLO). However, it remains still a challenge to obtain ideal perovskite NLO crystals featuring simultaneously large NLO coefficient, good optical transparency, high laser damage threshold, and stable physical and chemical properties, which are highly desirable for practical applications. Herein, a series is constructed of 1D chiral lead halide hybrid perovskites (R/S‐2‐MPD)PbX3 (2‐MPD = 2‐methylpiperidine; X = Cl, Br, I) featuring non‐centrosymmetric architectures. Among them, the (R/S‐2‐MPD)PbBr3 perovskites demonstrate superior performances in second‐order optical nonlinearity, including a large second‐harmonic generation coefficient (≈29.9 pm V–1), wide transparency region (λUV ≈ 310 nm), high laser damage threshold (≈2.84 mJ cm–2), high polarization ratio (up to 96%), and robust physical and chemical stabilities. Such a balanced performance of the chiral lead halide perovskites promises their advanced application in next‐generation photonics devices. [ABSTRACT FROM AUTHOR]