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Two SbX5-based isostructural polar 1D hybrid antimony halides with tunable broadband emission, nonlinear optics, and semiconductor properties

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Abstract

Metal halide perovskites based on MX6 (M is metal and X is halogen) octahedra have developed into significant materials, extensively used in many fields, such as solid-state lighting, semiconductor, and nonlinear optics. However, the MX5 square pyramid-based hybrid metal halides beyond zero-dimensional (0D) polyhedrons and clusters are rarely reported. Herein, we reported two new isostructural hybrid antimony halides, namely (2cepyH)SbCl4 (1-Cl) and (2cepyH)SbBr4 (2-Br) (2cepy = 1-(2-chloroethyl)pyrrolidine), characterized by 1D polar polyanionic chains formed by corner-sharing SbX5 tetragonal pyramid units. Upon photoexcitation at 340 nm, 1-Cl shows broad, yellow phosphorescence emissions stemming from triplet self-trapped excitons, as proved by its long lifetime (6.85 μs) and the temperature dependences of broadband emission. To our knowledge, this should be the first observation on the broadband emissive properties in the 1D hybrid metal halide constructed by MX5 tetragonal pyramid units. Moreover, second harmonic generation measurements show that the nonlinear optical properties of 2-Br (∼3.2 × KDP) are superior to that of 1-Cl (∼1.8 × KDP). Experimental and calculated data indicate that the bandgap of 1-Cl is larger than that of 2-Br and that the polar inorganic moieties determine their band structures. Our work opens up a new way for constructing broadband emission materials with novel polar frameworks.

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Acknowledgements

This work was supported by the Natural Science Foundation of China (21871167, 22075168), the 1331 Project of Shanxi Province, the Science and Technology Innovation Project in Colleges and Universities of Shanxi Province (2019L0451), and the Shanxi Normal University Startup. The authors would like to thank Prof. Zhenhua Qiao from University of Science and Technology of China for calculating the band structures and PDOS of two isostructural compounds presented in this work through using VASP software.

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Authors and Affiliations

  1. Key Laboratory of Magnetic Molecules & Magnetic Information Materials (Ministry of Education), Institute of Chemistry and Culture, School of Chemistry and Material Science, Shanxi Normal University, Linfen, 041004, China

    Zhikai Qi, Yali Chen, Huizhi Gao, Fu-Qiang Zhang, Shi-Li Li & Xian-Ming Zhang

  2. Key Laboratory of Interface Science and Engineering in Advanced Material (Ministry of Education), College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan, 030024, China

    Xian-Ming Zhang

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  1. Zhikai Qi
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  2. Yali Chen
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  4. Fu-Qiang Zhang
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Correspondence to Xian-Ming Zhang.

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Two SbX5-based isostructural polar 1D hybrid antimony halides with tunable broadband emission, nonlinear optics, and semiconductor properties

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Qi, Z., Chen, Y., Gao, H. et al. Two SbX5-based isostructural polar 1D hybrid antimony halides with tunable broadband emission, nonlinear optics, and semiconductor properties. Sci. China Chem. 64, 2111–2117 (2021). https://doi.org/10.1007/s11426-021-1076-9

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