Na 4 B 8 O 9 F 10 : A Deep-Ultraviolet Transparent Nonlinear Optical Fluorooxoborate with Unexpected Short Phase-Matching Wavelength Induced by Optimized Chromatic Dispersion.
Huanhuan ChengFuming LiZhi-Hua YangShilie PanPublished in: Angewandte Chemie (International ed. in English) (2022)
Exploring significant ultraviolet/deep-ultraviolet nonlinear optical (NLO) materials is hindered by rigorous and contradictory requirements, especially, possessing a moderate optical birefringence to meet phase-matching (PM). Except for suitable birefringence, small chromatic dispersion is also crucial to blue-shift the PM wavelength. Here, the introduction of a fluorinated tetrahedral boron-centred chromophore strategy was proposed to optimize the chromatic dispersion. Herein, the [BF 4 ] - unit with a large HOMO-LUMO band gap was introduced to the Na-B-O-F system and Na 4 B 8 O 9 F 10 was designed and synthesized successfully for the first time. Na 4 B 8 O 9 F 10 with an optimized chromatic dispersion can achieve a short second harmonic generation PM wavelength of 240 nm with a relatively small birefringence (0.036@1064 nm). Notably, Na 4 B 8 O 9 F 10 is the first acentric crystal with [BF 4 ] - units among the reported metal-fluorooxoborate systems, involving isolated [BF 4 ] - and novel [B 7 O 10 F 6 ] 5- fundamental building blocks.