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Pb3.5GeS4Br3: the first phase-matching thiogermanate halide infrared nonlinear optical material

Abstract

Two new thiohalides Pb3GeS4Br2 and Pb3.5GeS4Br3 have been synthesized by introducing Pb2+ into the thiogermanate system. The compounds crystallize in centrosymmetric P2(1)/c (Pb3GeS4Br2) and non-centrosymmetric P6(3) (Pb3.5GeS4Br3) space groups, respectively. To the best of our knowledge, Pb3GeS4Br2 and Pb3.5GeS4Br3 are the first Pb-containing thiogermanate halides, and the latter is the first phase-matching IR nonlinear optical material in the thiogermanate halide system. Due to the presence of Pb2+ with stereochemically active lone pair electrons, Pb3GeS4Br2 exhibits a strong optical anisotropy with a birefringence of 0.131@1064 nm, while Pb3.5GeS4Br3 shows a large second-harmonic generation response (0.8 x AgGaS2) and high laser-induced damage threshold (3.0 x AgGaS2). These results enrich the structural and chemical diversity of chalcohalides.

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date_range 2024
language English
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