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UV Solar‐Blind‐Region Phase‐Matchable Optical Nonlinearity and Anisotropy in a π‐Conjugated Cation‐Containing Phosphate
Author(s) -
Wu Chao,
Jiang Xingxing,
Wang Zujian,
Sha Hongyuan,
Lin Zheshuai,
Huang Zhipeng,
Long Xifa,
Humphrey Mark G.,
Zhang Chi
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202102992
Subject(s) - birefringence , ultraviolet , materials science , second harmonic generation , anisotropy , band gap , conjugated system , wavelength , phase (matter) , optoelectronics , analytical chemistry (journal) , optics , chemistry , polymer , laser , physics , organic chemistry , composite material
Wide ultraviolet (UV) transparency, strong second‐harmonic generation (SHG) response, and sufficient optical birefringence for phase‐matching (PM) at short SHG wavelengths are vital for practical UV nonlinear optical (NLO) materials. However, simultaneously optimizing these properties is a major challenge, particularly for metal phosphates. Herein, we report a non‐traditional π‐conjugated cation‐based UV NLO phosphate [C(NH 2 ) 3 ] 6 (PO 4 ) 2 ⋅3 H 2 O (GPO) with a short UV cutoff edge. GPO is SHG active at 1064 nm (3.8 × KH 2 PO 4 @ 1064 nm) and 532 nm (0.3 × β‐BaB 2 O 4 @ 532 nm) and also possesses a significant birefringence (0.078 @ 546 nm) with a band gap >6.0 eV. The PM SHG capability of GPO can extend to 250 nm, indicating GPO is a promising UV solar‐blind NLO material. Calculations and crystal structure analysis show that the rare coexistence of wide UV transparency, large SHG response, and optical anisotropy is due to the introduction of π‐conjugated cations [C(NH 2 ) 3 ] + and their favorable arrangement with [PO 4 ] 3− anions.