HgTeO 2 F(OH): A Nonlinear Optical Oxyfluoride Constructed of Active [TeO 2 F(OH)] 2- Pyramids and V-Shaped [HgO 2 ] 2- Groups.

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 Te 4+ lone-pair cation was introduced into oxyhalides, and one oxyfluoride, HgTeO 2 F(OH), was obtained via a hydrothermal reaction. Crystallized in the polar space group Pca 2 1 , the layered structure of HgTeO 2 F(OH) is composed of V-shaped [HgO 2 ] 2- groups and [TeO 2 F(OH)] 2- pyramids, in which the [TeO 2 F(OH)] 2- pyramid first served as the NLO functional motif. Its powder sample exhibits a phase-matchable SHG response of 1.1 × KH 2 PO 4 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 Te 4+ lone-pair cation makes the predominant contribution to the SHG effect and synergizes with the [HgO 2 ] 2- groups.