A new zero-dimensional（0D） thioborate Ba_9B_3GaS_（15） has been discovered by conventional high-temperature solid-state reaction. The compound crystallizes in orthorhombic space group Pbca with a = 8.4759（8）,b = ...A new zero-dimensional（0D） thioborate Ba_9B_3GaS_（15） has been discovered by conventional high-temperature solid-state reaction. The compound crystallizes in orthorhombic space group Pbca with a = 8.4759（8）,b = 22.266（2）,c = 31.426（3） ？,V = 5931（2） ？~3,Z = 8,Mr = 1819.11,Dc = 4.075 g/cm3,μ = 13.684 mm^（-1）,F（000） = 6320,S = 1.034,（Δρ）max = 5.039,（Δρ）min = –5.409 e/？~3,the final R = 0.0362 and w R = 0.1053 for 19243 observed reflections with I 〉 2σ（I）. The structure is constructed by discrete [BS_3]^（3–） trigonal planes and isolated [GaS_4]^（5–） tetrahedra with Ba^（2＋） and isolated S^（2–） filled among them. The UV-Vis-near-IR spectrum reveals a wide band gap of 3.15 eV that agrees with the electronic structure calculation.展开更多
Thioborates combine the advantages of sulfides and borates,and are a new type of multifunctional inorganic material with versatile structural features.Here,a thioborate KNa_(0.78)Eu_(0.27)In_(3.80)B_(12)S_(12) crystal...Thioborates combine the advantages of sulfides and borates,and are a new type of multifunctional inorganic material with versatile structural features.Here,a thioborate KNa_(0.78)Eu_(0.27)In_(3.80)B_(12)S_(12) crystallizing with a new type of compound was synthesized by a high-temperature flux method.Its structure features a rarely discovered B_(12)S_(12) cluster and diverse InSx(x=4,5,6)units built in a three-dimensional{[In3.80B_(12)S_(12)]2.6-}∞polyanionic framework.The structural complexity and novelty are well elaborated.Its optical band gap was determined to be 2.28 eV,and a theoretical calculation of its electronic structure was also performed.This work not only enriches the structural chemistry of chalcogenoborates but also provides a new potential RE-B-Q family(RE=rare-earth metal;Q=S,Se).The latter may produce some interesting functionals.展开更多
Exploration of new material systems and optical performance enhancement are huge challenges for the study of infrared nonlinear optical(IR NLO)materials.In this work,the first thioborate-thiogermanate and thioborate-t...Exploration of new material systems and optical performance enhancement are huge challenges for the study of infrared nonlinear optical(IR NLO)materials.In this work,the first thioborate-thiogermanate and thioborate-thiostannate compounds,Ca_(2)La(Ge_(0.72)Si_(0.28)S_(4))(BS_(3))and Ca_(2)La(Sn_(0.75)Si_(0.25)S_(4))(BS_(3)),containing both co-occupied Ca^(2+)/La^(3+)cation and[Ge/SiS_(4)]^(4-)or[Sn/SiS_(4)]^(4-)anion sites,respectively,were designed through an atomic site co-occupancy strategy.They inherited favourable 3D network structures in which the effectively aligned[MS_(4)]^(4-)and[BS_(3)]^(3-)functional anions were bridged by Ca^(2+)/La^(3+)cations.Remarkably,the title compounds achieved excellent IR NLO properties,including good chemical and thermal stabilities,wide light transmission ranges(0.45-11μm),strong second harmonic generation responses(1.5 and 2.0 times that of commercial AgGaS2 at 2.05μm)and high laser-induced damage thresholds(7 and 6 times that of AgGaS2).Theoretical calculation and experimental results revealed that,on the basis of excellent structural framework,introducing more active functional groups through atomic site co-occupancy could simultaneously enhance the second harmonic generation effect and maintain a relatively high laser-induced damage threshold.This work not only offers an easier synthetic route for mixed anionic thioborates but also provides inspiration for the design of well-performed NLO materials.展开更多
基金Supported by the National Natural Science Foundation of China(21233009,21225104,91422303,21301175 and 21171168)
文摘A new zero-dimensional（0D） thioborate Ba_9B_3GaS_（15） has been discovered by conventional high-temperature solid-state reaction. The compound crystallizes in orthorhombic space group Pbca with a = 8.4759（8）,b = 22.266（2）,c = 31.426（3） ？,V = 5931（2） ？~3,Z = 8,Mr = 1819.11,Dc = 4.075 g/cm3,μ = 13.684 mm^（-1）,F（000） = 6320,S = 1.034,（Δρ）max = 5.039,（Δρ）min = –5.409 e/？~3,the final R = 0.0362 and w R = 0.1053 for 19243 observed reflections with I 〉 2σ（I）. The structure is constructed by discrete [BS_3]^（3–） trigonal planes and isolated [GaS_4]^（5–） tetrahedra with Ba^（2＋） and isolated S^（2–） filled among them. The UV-Vis-near-IR spectrum reveals a wide band gap of 3.15 eV that agrees with the electronic structure calculation.
基金the financial support by the national natural science foundation of China(21771159,22071212)the Qinglan project from Yangzhou University.
文摘Thioborates combine the advantages of sulfides and borates,and are a new type of multifunctional inorganic material with versatile structural features.Here,a thioborate KNa_(0.78)Eu_(0.27)In_(3.80)B_(12)S_(12) crystallizing with a new type of compound was synthesized by a high-temperature flux method.Its structure features a rarely discovered B_(12)S_(12) cluster and diverse InSx(x=4,5,6)units built in a three-dimensional{[In3.80B_(12)S_(12)]2.6-}∞polyanionic framework.The structural complexity and novelty are well elaborated.Its optical band gap was determined to be 2.28 eV,and a theoretical calculation of its electronic structure was also performed.This work not only enriches the structural chemistry of chalcogenoborates but also provides a new potential RE-B-Q family(RE=rare-earth metal;Q=S,Se).The latter may produce some interesting functionals.
基金supported by the National Natural Science Foundation of China(No.22031009,22375201,and 21921001)the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(CXZX-2022-GH06).
文摘Exploration of new material systems and optical performance enhancement are huge challenges for the study of infrared nonlinear optical(IR NLO)materials.In this work,the first thioborate-thiogermanate and thioborate-thiostannate compounds,Ca_(2)La(Ge_(0.72)Si_(0.28)S_(4))(BS_(3))and Ca_(2)La(Sn_(0.75)Si_(0.25)S_(4))(BS_(3)),containing both co-occupied Ca^(2+)/La^(3+)cation and[Ge/SiS_(4)]^(4-)or[Sn/SiS_(4)]^(4-)anion sites,respectively,were designed through an atomic site co-occupancy strategy.They inherited favourable 3D network structures in which the effectively aligned[MS_(4)]^(4-)and[BS_(3)]^(3-)functional anions were bridged by Ca^(2+)/La^(3+)cations.Remarkably,the title compounds achieved excellent IR NLO properties,including good chemical and thermal stabilities,wide light transmission ranges(0.45-11μm),strong second harmonic generation responses(1.5 and 2.0 times that of commercial AgGaS2 at 2.05μm)and high laser-induced damage thresholds(7 and 6 times that of AgGaS2).Theoretical calculation and experimental results revealed that,on the basis of excellent structural framework,introducing more active functional groups through atomic site co-occupancy could simultaneously enhance the second harmonic generation effect and maintain a relatively high laser-induced damage threshold.This work not only offers an easier synthetic route for mixed anionic thioborates but also provides inspiration for the design of well-performed NLO materials.
