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Published on: April 14, 2020
Structural Evolution of Hybrid Bismuth-Based Halides toward Enhanced Second-Harmonic Generation Response and
Yi-Fan Fu1, Wen-Dong Yao1, Qiao-Feng Huang1
1School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, P. R. China.
Abstract:
Exploring new material systems with an enhancement of the birefringence and second harmonic generation (SHG) effect represents a highly worthwhile pursuit. Herein, three bismuth-based halides, centrosymmetric (CS) (SCN2H5)6BiBr6·Br3 (1), noncentrosymmetric (NCS) (NC2H8)4BiBr6·Br (2) and (NC2H8)2(N2H4CS)BiBr5 (3), were successfully designed through structural motif engineering. The regular full-halogen BiBr6 octahedron in 1 and 2 was successfully transferred to highly distorted heteroligand BiSBr5 octahedron in 3 via chemical substitution. Notably, the birefringence and SHG response of 3 are significantly enhanced to 0.118@546 nm and 2.1 × KDP, which are 5.4 and 2.6 times that of 2, respectively. Structural analysis and theory calculations reveal that the enhanced SHG intensity and birefringence of 3 can be attributed to the synergistic effect of unique heteroligand-coordinated [(N2H4CS)BiBr5]2- anions and organic NC2H8+ cations. This work not only discovers 3 as a promising nonlinear optical crystal but also provides an effective synthetic route for new metal halides with excellent optical properties.
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