Syntheses, Characterization, and Optical Properties of Centrosymmetric Ba 3 (BS 3 ) 1.5 (MS 3 ) 0.5 and Noncentrosymmetric Ba 3 (BQ 3 )(SbQ 3 )
2015; American Chemical Society; Volume: 54; Issue: 10 Linguagem: Inglês
10.1021/acs.inorgchem.5b00189
ISSN1520-510X
AutoresYanyan Li, Bingxuan Li, Ge Zhang, Liujiang Zhou, Hua Lin, Jinni Shen, Chengyi Zhang, Ling Chen, Li‐Ming Wu,
Tópico(s)Organometallic Compounds Synthesis and Characterization
ResumoThe most advanced UV–vis and IR NLO materials are usually borates and chalcogenides, respectively. But thioborates, especially thio-borometalates, are extremely rare. Here, four new such compounds are discovered by solid state reactions representing 0D structures constructed by isolated BQ3 trigonal planes and discrete MQ3 pyramids with Ba2+ cations filling among them, centrosymmetric monoclinic P21/c Ba3(BS3)1.5(MS3)0.5 (M = Sb, Bi) 1, 2 with a = 12.9255(9), 12.946(2) Å; b = 21.139(2), 21.170(2)Å; c = 8.4194(6), 8.4207(8) Å; β = 101.739(5), 101.688(7)°; V = 2252.3(3), 2259.9(3) Å3 and noncentrosymmetric hexagonal P6̅2m Ba3(BQ3)(SbQ3) (Q = S, Se) 3, 4 with a = b = 17.0560(9), 17.720(4) Å; c = 10.9040(9), 11.251(3) Å; V = 2747.1(3), 3060(2) Å3. 3 exhibits the strongest SHG among thioborates that is about three times that of the benchmark AgGaS2 at 2.05 μm. 1 and 3 also show an interesting structure relationship correlated to the size mismatching of the anionic building units that can be controlled by the experimental loading ratio of B:Sb. Syntheses, structure characterizations, and electronic structures based on the density functional theory calculations are reported.
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