HgTeO2F(OH): A Nonlinear Optical Oxyfluoride Constructed of Active [TeO2F(OH)]2- Pyramids and V-Shaped [HgO2]2- Groups

Ru-Ling Tang; Mei Yan; Wen-Dong Yao; Wenlong Liu; Sheng-Ping Guo

doi:10.1021/acs.inorgchem.1c03737

HgTeO₂F(OH): A Nonlinear Optical Oxyfluoride Constructed of Active [TeO₂F(OH)]^2- Pyramids and V-Shaped [HgO₂]^2- Groups

Inorg Chem. 2022 Jan 31;61(4):2333-2339. doi: 10.1021/acs.inorgchem.1c03737. Epub 2022 Jan 14.

Authors

Ru-Ling Tang¹, Mei Yan¹, Wen-Dong Yao¹, Wenlong Liu¹, Sheng-Ping Guo¹

Affiliation

¹ School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, P. R. China.

PMID: 35029377
DOI: 10.1021/acs.inorgchem.1c03737

Abstract

Oxyhalides possessing the merits of oxides and halides have widely received attention for their comprehensive physical performances, especially as potential nonlinear optical (NLO) crystals. Here, based on conventional strategy for obtaining acentric compounds, a Te⁴⁺ lone-pair cation was introduced into oxyhalides, and one oxyfluoride, HgTeO₂F(OH), was obtained via a hydrothermal reaction. Crystallized in the polar space group Pca2₁, the layered structure of HgTeO₂F(OH) is composed of V-shaped [HgO₂]^2- groups and [TeO₂F(OH)]^2- pyramids, in which the [TeO₂F(OH)]^2- pyramid first served as the NLO functional motif. Its powder sample exhibits a phase-matchable SHG response of 1.1 × KH₂PO₄ at 1064 nm, and its birefringence (0.09@1064 nm) is sufficient for phase-matchable behavior, which manifests its comprehensive capacity as a promising NLO candidate. Theoretical calculations about electronic structure and optical properties are also carried out, revealing that the Te⁴⁺ lone-pair cation makes the predominant contribution to the SHG effect and synergizes with the [HgO₂]^2- groups.