Two new members of zincoborate fluoride series Ba_(n+2)Zn_(n)(BO_(3))_(n)(B_(2)O_(5))F_(n)(n=1,2),namely,Ba_(3)Zn(BO_(3))(B_(2)O_(5))F and Ba_(4)Zn_(2)(BO_(3))2(B_(2)O_(5))F_(2)were firstly synthesized as high-quality...Two new members of zincoborate fluoride series Ba_(n+2)Zn_(n)(BO_(3))_(n)(B_(2)O_(5))F_(n)(n=1,2),namely,Ba_(3)Zn(BO_(3))(B_(2)O_(5))F and Ba_(4)Zn_(2)(BO_(3))2(B_(2)O_(5))F_(2)were firstly synthesized as high-quality single crystals via a hightemperature solution method by adjusting the molar ratios of reactants.They were structurally determined by single-crystal X-ray diffraction and their structures can be regarded as three dimensional(3D)framework stacking of^(2)_(∞)[Zn_(2)B_(6)O_(16)]^(10−)layers for Ba_(3)Zn(BO_(3))(B_(2)O_(5))F and^(2)_(∞)[Zn_(2)B_(4)O_(8)O_(5)/2O1/3]^(17/3−)layers for Ba_(4)Zn_(2)(BO_(3))_(2)(B_(2)O_(5))F_(2).To the best of our knowledge,the two title compounds are the first examples of two kinds of isolated B-O groups that coexist in one zincoborate halide.The structure comparisons were carried out among all the available anhydrous-zincoborates,and it is interesting to conclude that about 80%of zincoborates contain isolated B-O clusters and notably the molar ratio of cation/boron(A/B)affects the polymerization of isolated B-O configuration.What’s more,the first-principles calculations,infrared spectra,and UV-vis-NIR diffuse reflectance spectra of title compounds have also been performed.展开更多
Ultraviolet nonlinear optical (UV NLO) crystals are the key and basic materials for solid-state lasers.Phosphates as UV NLO crystals are limited in practical applications due to their weak second-harmonic generation (...Ultraviolet nonlinear optical (UV NLO) crystals are the key and basic materials for solid-state lasers.Phosphates as UV NLO crystals are limited in practical applications due to their weak second-harmonic generation (SHG) response.In this work,two non-centrosymmetric pyro-phosphates of K_(3)SrBi(P_(2)O_(7))_(2) and Rb_(3)SrBi(P_(2)O_(7))_(2) have been synthesized by a high-temperature solution method.Systematic property measurements show that they both have short UV cut-off edges (∼240 nm) and large SHG responses (4 × KDP for K_(3)SrBi(P_(2)O_(7))_(2) and 2.1 × KDP for Rb_(3)SrBi(P_(2)O_(7))_(2)).Thus,they are both promising UV NLO candidates.In particular,K_(3)SrBi(P_(2)O_(7))_(2) shows the strongest SHG response in the family of A_(3)BBi(P_(2)O_(7))_(2) (A = K,Rb,B = Sr;A = Rb,Cs,B = Ba,Pb),which is about twice higher than that of isomorphic Rb_(3)SrBi(P_(2)O_(7))_(2).The study of the structure–property relationship shows that the synergistic effect of P_(2)O_(7) dimers and BiO6 polyhedra is the main contribution to their excellent NLO properties.And better orientations of P_(2)O_(7) dimers and larger distortion of BiO6 units play important roles in enhancing the SHG response of K_(3)SrBi(P_(2)O_(7))_(2).展开更多
Three Pb_(5)Zn_(4)B_(6)O_(18)polymorphs were synthesized by a high temperature solution method.Their structures were determined using single crystal X-ray diffraction and they crystallize in P21/c forα-,γ-Pb_(5)Zn_(...Three Pb_(5)Zn_(4)B_(6)O_(18)polymorphs were synthesized by a high temperature solution method.Their structures were determined using single crystal X-ray diffraction and they crystallize in P21/c forα-,γ-Pb_(5)Zn_(4)B_(6)O_(18)and P1forβ-Pb_(5)Zn_(4)B_(6)O_(18).It is interesting thatα-andβ-Pb_(5)Zn_(4)B_(6)O_(18)crystallize in different space groups with similar structures andα-andγ-Pb_(5)Zn_(4)B_(6)O_(18)crystallize in the same space group with totally different structures.Inα-andβ-Pb_(5)Zn_(4)B_(6)O_(18),ZnO_(4)tetrahedra connect with isolated BO_(3)triangles to construct two dimensional(2D)layers,while inγ-Pb_(5)Zn_(4)B_(6)O_(18),2D Zn-B-O layers change to the 3D framework.The phase transformations of Pb_(5)Zn_(4)B_(6)O_(18)are investigated by the combination of powder X-ray diffraction,thermal behavior analysis and theoretical simulation.Additional functional properties have been investigated using methods such as including UV-vis-NIR diffuse reflectance and IR spectroscopy.展开更多
A new complex alkaline-earth metal borosilicate chloride Ba_(3)Ca4(BO_(3))_(3)(SiO4)Cl has been successfully synthesized by the high-temperature solution method.It crystallizes in the space group P6_(3)mc(no.186)of th...A new complex alkaline-earth metal borosilicate chloride Ba_(3)Ca4(BO_(3))_(3)(SiO4)Cl has been successfully synthesized by the high-temperature solution method.It crystallizes in the space group P6_(3)mc(no.186)of the hexagonal system.展开更多
A new alkali metal borate fluoride Li_(3)KB_(9)O_(15)F has been successfully obtained by the high-temperature solution method in open air for the first time.An X-ray crystallographic study reveals that it crystallizes...A new alkali metal borate fluoride Li_(3)KB_(9)O_(15)F has been successfully obtained by the high-temperature solution method in open air for the first time.An X-ray crystallographic study reveals that it crystallizes in the trigonal space group R3c(no.161),a=11.974(4)Å,b=11.974(4)Å,c=15.998(11)Åand Z=6.It exhibits a complicated three-dimensional(3D)network composed of LiO_(3)F,KO_(6)F distorted polyhedra and 3D B–O framework.展开更多
A new member in the bariumfluorooxoborate family,namely Ba_(2)B_(7)O_(12)F,was obtained by the high-temp erature solution method in an open system under ambient pressure.The structure features a new funda mental build...A new member in the bariumfluorooxoborate family,namely Ba_(2)B_(7)O_(12)F,was obtained by the high-temp erature solution method in an open system under ambient pressure.The structure features a new funda mental building block[B_(7)O_(16)F],which interconnects with each other to form the anionic framework[B_(7)O_(12)F]∞with two different caves in which the cations reside.The experiment result indicates that Ba_(2)B_(7)O_(12)F possesses a deep-ultraviolet cut-offedge below 180 nm.展开更多
基金gratefully acknowledge financial support for this work from the National Natural Science Foundation of China(Grant No.51425206,21501194)Xinjiang Key Laboratory Foundation(Grant No.2014KL009)+2 种基金the National Key Research Projects(Grant No.2016YFB1102300,SQ2016YFGX070132)the Key Laboratory Foundation for Functional Materials and Devices for Special Environments of CAS(Grant No.2013DP173196-2013-01)the Xinjiang Program of Cultivation of Young Innovative Technical Talents(Grant No.2014731026).
文摘Two new members of zincoborate fluoride series Ba_(n+2)Zn_(n)(BO_(3))_(n)(B_(2)O_(5))F_(n)(n=1,2),namely,Ba_(3)Zn(BO_(3))(B_(2)O_(5))F and Ba_(4)Zn_(2)(BO_(3))2(B_(2)O_(5))F_(2)were firstly synthesized as high-quality single crystals via a hightemperature solution method by adjusting the molar ratios of reactants.They were structurally determined by single-crystal X-ray diffraction and their structures can be regarded as three dimensional(3D)framework stacking of^(2)_(∞)[Zn_(2)B_(6)O_(16)]^(10−)layers for Ba_(3)Zn(BO_(3))(B_(2)O_(5))F and^(2)_(∞)[Zn_(2)B_(4)O_(8)O_(5)/2O1/3]^(17/3−)layers for Ba_(4)Zn_(2)(BO_(3))_(2)(B_(2)O_(5))F_(2).To the best of our knowledge,the two title compounds are the first examples of two kinds of isolated B-O groups that coexist in one zincoborate halide.The structure comparisons were carried out among all the available anhydrous-zincoborates,and it is interesting to conclude that about 80%of zincoborates contain isolated B-O clusters and notably the molar ratio of cation/boron(A/B)affects the polymerization of isolated B-O configuration.What’s more,the first-principles calculations,infrared spectra,and UV-vis-NIR diffuse reflectance spectra of title compounds have also been performed.
基金supported by the Natural Science Foundation of Tianjin(Grant No.20JCJQJC00060 and 19JCZDJC38200)the National Natural Science Foundation of China(Grant No.22071179,51802217,51972230,61835014,and 51890865)+1 种基金Tianjin Science and technology Plan Program(Grant No.19ZYPTJC00070)National Key R&D Program of China(Grant No.2016YFB0402103).
文摘Ultraviolet nonlinear optical (UV NLO) crystals are the key and basic materials for solid-state lasers.Phosphates as UV NLO crystals are limited in practical applications due to their weak second-harmonic generation (SHG) response.In this work,two non-centrosymmetric pyro-phosphates of K_(3)SrBi(P_(2)O_(7))_(2) and Rb_(3)SrBi(P_(2)O_(7))_(2) have been synthesized by a high-temperature solution method.Systematic property measurements show that they both have short UV cut-off edges (∼240 nm) and large SHG responses (4 × KDP for K_(3)SrBi(P_(2)O_(7))_(2) and 2.1 × KDP for Rb_(3)SrBi(P_(2)O_(7))_(2)).Thus,they are both promising UV NLO candidates.In particular,K_(3)SrBi(P_(2)O_(7))_(2) shows the strongest SHG response in the family of A_(3)BBi(P_(2)O_(7))_(2) (A = K,Rb,B = Sr;A = Rb,Cs,B = Ba,Pb),which is about twice higher than that of isomorphic Rb_(3)SrBi(P_(2)O_(7))_(2).The study of the structure–property relationship shows that the synergistic effect of P_(2)O_(7) dimers and BiO6 polyhedra is the main contribution to their excellent NLO properties.And better orientations of P_(2)O_(7) dimers and larger distortion of BiO6 units play important roles in enhancing the SHG response of K_(3)SrBi(P_(2)O_(7))_(2).
基金supported by the Key Research Project of Frontier Science of CAS(Grant No.QYZDB-SSW-JSC049)the Western Light Foundation of CAS(Grant 2016-QNXZ-A-2)+2 种基金the Xinjiang Scientific and Technological Innovation Talents Project(Grant No.QN2016YX0339)the Xinjiang International Science&Technology Cooperation Program(Grant No.2017E01014)the Youth Innovation Promotion Association CAS(Grant No.2015353).
文摘Three Pb_(5)Zn_(4)B_(6)O_(18)polymorphs were synthesized by a high temperature solution method.Their structures were determined using single crystal X-ray diffraction and they crystallize in P21/c forα-,γ-Pb_(5)Zn_(4)B_(6)O_(18)and P1forβ-Pb_(5)Zn_(4)B_(6)O_(18).It is interesting thatα-andβ-Pb_(5)Zn_(4)B_(6)O_(18)crystallize in different space groups with similar structures andα-andγ-Pb_(5)Zn_(4)B_(6)O_(18)crystallize in the same space group with totally different structures.Inα-andβ-Pb_(5)Zn_(4)B_(6)O_(18),ZnO_(4)tetrahedra connect with isolated BO_(3)triangles to construct two dimensional(2D)layers,while inγ-Pb_(5)Zn_(4)B_(6)O_(18),2D Zn-B-O layers change to the 3D framework.The phase transformations of Pb_(5)Zn_(4)B_(6)O_(18)are investigated by the combination of powder X-ray diffraction,thermal behavior analysis and theoretical simulation.Additional functional properties have been investigated using methods such as including UV-vis-NIR diffuse reflectance and IR spectroscopy.
基金supported by the Key Research Project of Frontier Science of CAS(Grant No.QYZDB-SSW-JSC049)the National Natural Science Foundation of China(Grant No.61835014 and 51425206)+1 种基金the National Key Research Project(Grant No.2016YFB0402104)the Youth Innovation Promotion Association of CAS(Grant No.2012305).
文摘A new complex alkaline-earth metal borosilicate chloride Ba_(3)Ca4(BO_(3))_(3)(SiO4)Cl has been successfully synthesized by the high-temperature solution method.It crystallizes in the space group P6_(3)mc(no.186)of the hexagonal system.
基金supported by the Xinjiang International Science&Technology Cooperation Program(Grant No.2017E01014)Tianshan Innovation Team Program(Grant No.2018D14001)the National Natural Science Foundation of China(Grant No.U1703132)+6 种基金the Tianshan Xue Song Program“Xinjiang Youth Top Talent Backup Project”(Grant No.2017XS17),the National Key Research Project(Grant No.2016YFB1102302,2016YFB0402104)the Science and Technology Project of Urumqi(Grant No.P161010002)the Xinjiang Key Research and Development Program(Grant No.2016B02021)the Major Program of Xinjiang Uygur Autonomous Region of China during the 13th Five-Year Plan Period(Grant No.2016A02003)the West Light Foundation of the Chinese Academy of Sciences(Grant No.2016-YJRC-2)the Foundation of Director of XTIPC,CAS(Grant No.2016PY004)the Tianshan Xue Song Program“Xinjiang Youth Top Talent Backup Project”(Grant No.2017XS17).
文摘A new alkali metal borate fluoride Li_(3)KB_(9)O_(15)F has been successfully obtained by the high-temperature solution method in open air for the first time.An X-ray crystallographic study reveals that it crystallizes in the trigonal space group R3c(no.161),a=11.974(4)Å,b=11.974(4)Å,c=15.998(11)Åand Z=6.It exhibits a complicated three-dimensional(3D)network composed of LiO_(3)F,KO_(6)F distorted polyhedra and 3D B–O framework.
基金supported by the National Natural Science Foundation of China(U1703132,51872325,61835014 and 51972336)Tianshan Innovation Team Program(2018D14001)+1 种基金Xinjiang International Science&Technology Cooperation Program(2017E01014 and 2017E01013)Fujian Innovation Academy,CAS and the National Key Research Project(2016YFB0402104).
文摘A new member in the bariumfluorooxoborate family,namely Ba_(2)B_(7)O_(12)F,was obtained by the high-temp erature solution method in an open system under ambient pressure.The structure features a new funda mental building block[B_(7)O_(16)F],which interconnects with each other to form the anionic framework[B_(7)O_(12)F]∞with two different caves in which the cations reside.The experiment result indicates that Ba_(2)B_(7)O_(12)F possesses a deep-ultraviolet cut-offedge below 180 nm.
