Birefringent materials possess significant optical anisotropy,making them pivotal in modulating light polarization,particularly in laser technology and scientific applications.In this study,five variants of antimony p...Birefringent materials possess significant optical anisotropy,making them pivotal in modulating light polarization,particularly in laser technology and scientific applications.In this study,five variants of antimony potassium fluoronitrates named SbF_(3)·KNO_(3)(1),SbF_(3)·3KNO_(3)(2),SbF_(3)·3KSbF_(4)·KNO_(3)(3),KSb_(2)F_(7)·3KNO_(3)(4),and KSb_(2)F_(7)·2KNO_(3)(5)were obtained.Remarkably,each compound contains distinct Sb-polyhedra configurations.Compounds 1 and 2 consist of singular[SbF_(3)]units,compound 3 harbors a mixture of[SbF_(3)]and[SbF_(4)]units,while compounds 4 and 5 feature single[SbF_(4)]units.Interestingly,the birefringence escalates progressively from 1 to 5,and notably,compound 5 exhibits the most pronounced birefringence among all reported inorganic antimony oxysalts.Detailed structural and property analyses affirm that the structural variance among the five compounds underpins the observed differences in birefringence.Moreover,the synergistic interplay between planarπ-conjugated NO_(3)^(−)groups and Sb^(3+)ions with lone-pair electrons facilitates the emergence of substantial polarization anisotropy.展开更多
Herein,two antimony sulfates,named RbSb(SO_(4))_(2)(1)and CsSb(SO_(4))_(2)(2),have been successfully synthesized with the introduction of Sb^(3+)cation with stereochemically active lone pairs(SCALP)into sulfates by th...Herein,two antimony sulfates,named RbSb(SO_(4))_(2)(1)and CsSb(SO_(4))_(2)(2),have been successfully synthesized with the introduction of Sb^(3+)cation with stereochemically active lone pairs(SCALP)into sulfates by the conventional hydrothermal method.Both two compounds endow short ultraviolet(UV)absorption edges(281 nm and 278 nm,respectively)and large birefringence(0.171@546 nm and 0.174@546 nm,respectively),which means that they are promising short-wave UV optical materials.Interestingly,though both of the two compounds exhibit similar 1D chained structures,and possess the same functional moieties including SbO4 seesaws and SO4 tetrahedral groups,they exhibit significantly opposite macroscopic symmetries,i.e.,compound 1 crystallizes in a centrosymmetric(CS)manner(P2_(1)/n)and compound 2 in a noncentrosymmetric(NCS)manner(P2_(1)2_(1)2_(1)),due to the size of cations[r(Rb+)=1.56 A˚,r(Cs+)=1.67 A˚]affects the orientation of SCALP of the adjacent Sb^(3+).展开更多
Finding suitable strategies to effectively enhance the optical properties of materials are the goal being pursued by researchers.Herein,cation-anion synergetic interactions strategy was proposed to develop two novel o...Finding suitable strategies to effectively enhance the optical properties of materials are the goal being pursued by researchers.Herein,cation-anion synergetic interactions strategy was proposed to develop two novel organic-inorganic hybrid antimony-based optical materials,(C_(3)H_(5)N_(2))Sb F_(2)SO_(4)(I)and(C_(5)H_(6)N)Sb F_(2)SO_(4)(Ⅱ),which were obtained by introducing Sb^(3+)cation containing stereochemically active lone-pair(SCALP)and organicπ-conjugated cations into sulphate system.The synergistic interactions of the organicπ-conjugated cations,the inorganic[SbO_(2)F_(2)]^(3-)seesaw anions and the[SO_(4)]^(2-)distorted tetrahedra anions make their ultraviolet(UV)absorption edges approach 297 and 283 nm,respectively,and raise their birefringence up to 0.193@546 nm and 0.179@546 nm,respectively.Interestingly,although the two compounds have the same stoichiometric ratio and similar one-dimensional(1D)chain structure,they show opposite macroscopic symmetry,where the NCS compound(Ⅱ)exhibits a large secondharmonic generation(SHG)response(1.6 times that of KH_(2)PO_(4)).The two reported compounds are found to be promising UV optical materials in the experimental tests.展开更多
Birefringent materials with large optical anisotropy,which can be used to modulate the polarization of light,play a key role in laser techniques and science.However,the exploration studies of new,superior birefringent...Birefringent materials with large optical anisotropy,which can be used to modulate the polarization of light,play a key role in laser techniques and science.However,the exploration studies of new,superior birefringent materials develop extremely slowly due to the lack of effective guidelines for rational design.Herein,three antimony(Ⅲ)fluoride oxalates,namely,Na_(2)Sb_(2)(C_(2)O_(4))F_(6),K_(2)Sb_(2)(C_(2)O_(4))F_(6),and Cs_(2)Sb_(2)-(C_(2)O_(4))_(2)F_(4)·H_(2)O,were successfully synthesized through a rational combination ofπ-conjugated C_(2)O_(4)^(2-)anions and Sb^(3+)cations with stereochemically active lone pairs.These oxalates feature unique quasi-one-dimensional chain structures that induce large optical anisotropy.Remarkably,Cs_(2)Sb_(2)(C_(2)O_(4))_(2)-F_(4)·H_(2)O exhibits the largest birefringence(0.325@546 nm)among all reported antimony(Ⅲ)-based oxysalts.Detailed structural analysis and theoretical calculations confirmed that the optical anisotropy of these oxalates could be tuned through the synergetic interactions of templated cations and anionic functional groups.This work may open the door to efficiently designing excellent birefringent materials and guide the further discovery of other novel structure-driven functional materials.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22122106,22071158,22375139,22305166).
文摘Birefringent materials possess significant optical anisotropy,making them pivotal in modulating light polarization,particularly in laser technology and scientific applications.In this study,five variants of antimony potassium fluoronitrates named SbF_(3)·KNO_(3)(1),SbF_(3)·3KNO_(3)(2),SbF_(3)·3KSbF_(4)·KNO_(3)(3),KSb_(2)F_(7)·3KNO_(3)(4),and KSb_(2)F_(7)·2KNO_(3)(5)were obtained.Remarkably,each compound contains distinct Sb-polyhedra configurations.Compounds 1 and 2 consist of singular[SbF_(3)]units,compound 3 harbors a mixture of[SbF_(3)]and[SbF_(4)]units,while compounds 4 and 5 feature single[SbF_(4)]units.Interestingly,the birefringence escalates progressively from 1 to 5,and notably,compound 5 exhibits the most pronounced birefringence among all reported inorganic antimony oxysalts.Detailed structural and property analyses affirm that the structural variance among the five compounds underpins the observed differences in birefringence.Moreover,the synergistic interplay between planarπ-conjugated NO_(3)^(−)groups and Sb^(3+)ions with lone-pair electrons facilitates the emergence of substantial polarization anisotropy.
基金the National Natural Science Foundation of China(Nos.22122106,22071158,21971171)the Fundamental Research Funds from Sichuan University(No.2021SCUNL101).
文摘Herein,two antimony sulfates,named RbSb(SO_(4))_(2)(1)and CsSb(SO_(4))_(2)(2),have been successfully synthesized with the introduction of Sb^(3+)cation with stereochemically active lone pairs(SCALP)into sulfates by the conventional hydrothermal method.Both two compounds endow short ultraviolet(UV)absorption edges(281 nm and 278 nm,respectively)and large birefringence(0.171@546 nm and 0.174@546 nm,respectively),which means that they are promising short-wave UV optical materials.Interestingly,though both of the two compounds exhibit similar 1D chained structures,and possess the same functional moieties including SbO4 seesaws and SO4 tetrahedral groups,they exhibit significantly opposite macroscopic symmetries,i.e.,compound 1 crystallizes in a centrosymmetric(CS)manner(P2_(1)/n)and compound 2 in a noncentrosymmetric(NCS)manner(P2_(1)2_(1)2_(1)),due to the size of cations[r(Rb+)=1.56 A˚,r(Cs+)=1.67 A˚]affects the orientation of SCALP of the adjacent Sb^(3+).
基金supported by the National Natural Science Foundation of China(Nos.22122106,22071158,21971171,22305166)the Fundamental Research Funds from Sichuan University(No.2021SCUNL101)the Natural Science Foundation of Sichuan Province(No.2023NSFC1066)。
文摘Finding suitable strategies to effectively enhance the optical properties of materials are the goal being pursued by researchers.Herein,cation-anion synergetic interactions strategy was proposed to develop two novel organic-inorganic hybrid antimony-based optical materials,(C_(3)H_(5)N_(2))Sb F_(2)SO_(4)(I)and(C_(5)H_(6)N)Sb F_(2)SO_(4)(Ⅱ),which were obtained by introducing Sb^(3+)cation containing stereochemically active lone-pair(SCALP)and organicπ-conjugated cations into sulphate system.The synergistic interactions of the organicπ-conjugated cations,the inorganic[SbO_(2)F_(2)]^(3-)seesaw anions and the[SO_(4)]^(2-)distorted tetrahedra anions make their ultraviolet(UV)absorption edges approach 297 and 283 nm,respectively,and raise their birefringence up to 0.193@546 nm and 0.179@546 nm,respectively.Interestingly,although the two compounds have the same stoichiometric ratio and similar one-dimensional(1D)chain structure,they show opposite macroscopic symmetry,where the NCS compound(Ⅱ)exhibits a large secondharmonic generation(SHG)response(1.6 times that of KH_(2)PO_(4)).The two reported compounds are found to be promising UV optical materials in the experimental tests.
基金supported by the National Natural Science Foundation of China(22122106,22071158,21971171,and21875146)National Research Foundation of Korea(NRF)funded by the Ministry of Science and International Cooperation of Technology(2019R1A2C3005530)。
文摘Birefringent materials with large optical anisotropy,which can be used to modulate the polarization of light,play a key role in laser techniques and science.However,the exploration studies of new,superior birefringent materials develop extremely slowly due to the lack of effective guidelines for rational design.Herein,three antimony(Ⅲ)fluoride oxalates,namely,Na_(2)Sb_(2)(C_(2)O_(4))F_(6),K_(2)Sb_(2)(C_(2)O_(4))F_(6),and Cs_(2)Sb_(2)-(C_(2)O_(4))_(2)F_(4)·H_(2)O,were successfully synthesized through a rational combination ofπ-conjugated C_(2)O_(4)^(2-)anions and Sb^(3+)cations with stereochemically active lone pairs.These oxalates feature unique quasi-one-dimensional chain structures that induce large optical anisotropy.Remarkably,Cs_(2)Sb_(2)(C_(2)O_(4))_(2)-F_(4)·H_(2)O exhibits the largest birefringence(0.325@546 nm)among all reported antimony(Ⅲ)-based oxysalts.Detailed structural analysis and theoretical calculations confirmed that the optical anisotropy of these oxalates could be tuned through the synergetic interactions of templated cations and anionic functional groups.This work may open the door to efficiently designing excellent birefringent materials and guide the further discovery of other novel structure-driven functional materials.
