In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.The...In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.There are rare examples where the 9-BBN derivatives serve as the potentially diverse C8 building blocks in cross-coupling reactions.Herein,we report a cobalt-catalyzed migratory carboncarbon cross-coupling reaction of the in situ formed 9-BBN ate complexes to afford diverse aryl-and alkyl-functionalized cyclooctenes.Preliminary mechanistic studies suggest the oxidation-induced cisbicyclo[3.3.0]oct-1-ylborane is the key intermediate in this migratory cross-coupling reaction,which promotes the development of other diverse migratory cross-coupling of borate complexes.展开更多
The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic...The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic frameworks formed by B–O and B–O–F units significantly determine the physical properties of fluorooxoborates.Therefore,the rational design of anionic frameworks could facilitate the materials discovery process.Herein,we propose that a candidate anionic framework can be efficiently derived from an existing one by slightly altering its oxygen content.Following this idea,we hypothesized the existence of a 1D[B_(3)O_(5)F]_(∞)chain from the wellknown 2D[B_(6)O_(9)F_(2_)]_(∞)layer.Accordingly,seven CaB_(3)O_(5)F structures with the expected anionic framework were successfully predicted.First-principles calculations show that all these structures have potential in the UV/DUV birefringent or nonlinear optical(NLO)material field,indicating that the 1D[B_(3)O_(5)F]_(∞)chain is indeed a promising anionic framework for achieving UV/DUV birefringent and NLO performance.展开更多
Two new isostructural multi-metal beryllium borates, m^3 Li Na4Be4B10O24F（M = Sr（1）, Cd（2））, have been synthesized by spontaneous crystallization. The structures were verified by single-crystal X-ray crystallogr...Two new isostructural multi-metal beryllium borates, m^3 Li Na4Be4B10O24F（M = Sr（1）, Cd（2））, have been synthesized by spontaneous crystallization. The structures were verified by single-crystal X-ray crystallography. The compounds crystallize in the trigonal space group R 3, with a = b = 9.4645（1） A, c = 38.842（8） A, V = 3013.2（6） A3, Z = 6, F（000） = 2568, Dc = 3.005 g/cm^3, Mr = 908.9, R = 0.0327, w R = 0.0678, μ = 8.160 mm-1 for Sr3 Li Na4Be4B10O24F and a = b = 9.3019（8） A, c = 37.782（7） A, V = 2831.12（9） A3, Z = 6, F（000） = 2748, Dc = 3.459 g/cm^3, Mr = 983.24, R = 0.0158, w R = 0.0455, μ = 3.586 mm-1 for Cd3 Li Na4Be4B10O24F. The structures are characterized by an infinite two-dimensional [Be8B16O40F2]∞ double layer bridged by [B12O24] groups like a sandwich structure, while the cations reside in tunnels along different directions. UV-vis-IR diffuse reflectance spectroscopy demonstrates that their cut-off edges are below 200 nm. Thermal analysis shows that they melt incongruently and their melting points are around 740-770 ℃.展开更多
This paper is devoted to the rare-earth borates described by the general formula RM3（BO3）4, M = Al, Fe, and Cr, that have non-centrosymmetric trigonal slructure of the natural mineral huntite. It give a brief review...This paper is devoted to the rare-earth borates described by the general formula RM3（BO3）4, M = Al, Fe, and Cr, that have non-centrosymmetric trigonal slructure of the natural mineral huntite. It give a brief review of a spectroscopic research on YbAI3（BO3）4 （YbAB）, on a large group of magnetic iron borates, and on NdCra（BO3）4.展开更多
1 Introduction Lithium and its compounds as national strategic resources are extensively used in national defense,industrial and agricultural production.As we know,the salt lakes in the western of China are famous for...1 Introduction Lithium and its compounds as national strategic resources are extensively used in national defense,industrial and agricultural production.As we know,the salt lakes in the western of China are famous for its high展开更多
Amounts of lithium-containing salt lake brine resources are widely distributed in the four provinces named Qinghai,Tibet,Inner Mongolia and Xinjiang province,especially the salt lakes in Qinghai-Tibet Plateau are abun...Amounts of lithium-containing salt lake brine resources are widely distributed in the four provinces named Qinghai,Tibet,Inner Mongolia and Xinjiang province,especially the salt lakes in Qinghai-Tibet Plateau are abundant of展开更多
It is well known that boron exists as polyborate anions in aqueous solution.Boron atom can coordinates to three or four oxygen atoms and borate can exist as not only the monomer but also the polymer.The polymerization
Two new nonmetal borates, [（C2H10N2）]2[B14O20（OH）6] 1 and [C8H22N4][B5O6（OH）4]2 2, have been synthesized under mild conditions and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis and ...Two new nonmetal borates, [（C2H10N2）]2[B14O20（OH）6] 1 and [C8H22N4][B5O6（OH）4]2 2, have been synthesized under mild conditions and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis and thermogravimetric analysis. Crystal data for compound 1： triclinic, space group P^-1, a = 8.4979（17）, b = 8.8498（18）, c = 10.065（2）A^°, α = 95.01（3）, β = 96.99（3）, γ = 116.82（3）°, V= 661.8（3）A^°^3, Z= 1, Mr = 697.63, Dc = 1.751 g/cm^3,μ = 0.163 mm^-1, F（000） = 356, the final R = 0.0372 and wR = 0.0968 （I 〉 2σ（I））; and those for compound 2： monoclinic, space group P21/c, a = 9.1867（18）, b= 14.118（3）, c = 10.334（2）A^°, β = 91.48（3）°, V = 1339.8（5）A^°^3, Z = 2, Mr = 610.46, Dc = 1.513 g/cm^3,μ = 0.135 mm^-1, F（000） = 632, the final R = 0.0350 and wR = 0.0912 （I 〉 2σ（I））. For both 1 and 2, the anionic units are interlinked via O-H…O hydrogen bonds to form a 3D supramolecular network, while the protonated cations are located in the free space of the inorganic borate framework and interact with the anions by electrostatic attraction and extensive N-H…O hydrogen bonds.展开更多
The antiwear and friction-reducing performances of sodium borate, potassium borate and lanthanum chloride in water were evaluated on a four-ball friction tester. The topographies, element distribution and chemical cha...The antiwear and friction-reducing performances of sodium borate, potassium borate and lanthanum chloride in water were evaluated on a four-ball friction tester. The topographies, element distribution and chemical characteristics of the worn surfaces were investigated by scanning electron microscope （SEM）, energy dispersion of X-ray （EDX） and X-ray photoelectron spectroscope （XPS）. The results indicated that sodium borate, potassium borate and lanthanum chloride increased extreme pressure, antiwear and friction-reducing capacities of water to a certain extent, of which potassium borate was the best candidate. Combination of lanthanum chloride with sodium borate and po- tassium borate respectively further improved antiwear and friction-reducing capacities. Scratches of worn surfaces lubricated with water containing borates and lanthanum chloride were less severe than those lubricated with water containing borates alone. A tribochemical film mainly composed of oxides of lanthanum, boron and iron reduced friction and wear for water lubricant formulated with both borates and lanthanum chloride.展开更多
A benzotriazole-containing derivative was synthesized via the Mannich reaction.The structure was characterized by NMR spectroscopy.By utilizing computational chemistry and molecular simulation,the calculation and mapp...A benzotriazole-containing derivative was synthesized via the Mannich reaction.The structure was characterized by NMR spectroscopy.By utilizing computational chemistry and molecular simulation,the calculation and mapping of atomic charge and frontier molecular orbitals with complex structure of the borate were carried out.The acid number of BTBE(nitrogen-containing heterocyclic borate)was determined by the standard test method for acid number and the open observation method.The results showed that BTBE had a low initial acid number,because the acid number was changed only after 72 hours of hydrolysis,and it was negative after the hydrolysis reached 120 hours.The extreme-pressure friction resistance of BTBE and other four base oils was also determined.For 5 kinds of base oils,the friction experiment was carried out under a load of 30 kgf,and the BTBE showed a lowest wear scar diameter(0.365 mm)along with a highest maximum non-seizure load.The results showed that the EP friction resistance of BTBE was stronger than that of other four base oils under the same test conditions.The results of hydrolysis performance showed that the synthesized nitrogencontaining heterocyclic borate had a high resistance to hydrolysis,while demonstrating broad application prospects.展开更多
Two new borate compounds, C4H10N2·B6O8（OH）2 and （NH3CH2CH2NH3）B5O8 （OH）2, have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, elemental analysis and...Two new borate compounds, C4H10N2·B6O8（OH）2 and （NH3CH2CH2NH3）B5O8 （OH）2, have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, elemental analysis and thermal analysis. Compound 1 crystallizes in the monoclinic system, space group P21/c, with a = 8.3318（17）, b = 6.2118（12）, c = 12.479（3） A, β = 108.96（3）°, V = 610.8（2） A^3, Mr = 313.02, Z = 2, 13,.= 1.702 g/cm^,/J = 0.150 mm^-1, F（000） = 320, R = 0.0387 and wR = 0.0924. Its layered structure is linked by infinite covalently coordinated neutral sheets with 3,20-membered window system, which are built up from alternative B6O8（OH）2 subunits donated by two piperzazine nitrogen donors. 2 crystallizes in monoclinic, space group Co, with a = 6.7207（13）, b = 11.481 （2）, c = 12.564（3）A,β = 95.25（3）°, V = 965.4（3） A^3, Mr = 261.18, Z = 4, Dc = 1.797 g/cm^3,/t = 0.164 mm^-1, F（000） = 536, R = 0.0396 and wR = 0.0752. Its oxoborate structure is generated from the sheets of 3,9-membered boron rings bonded diamine molecules through electrostatic and H-bonding interactions to form a two-dimensional layered network.展开更多
Exploration of short-wave ultraviolet beryllium-free Sr_(2)Be_(2)B_(2)O_(7)-type borates is of great significance to the development of short-wave ultraviolet lasers.As a structural analogy to BeO_(4),the ZnO_(4) unit...Exploration of short-wave ultraviolet beryllium-free Sr_(2)Be_(2)B_(2)O_(7)-type borates is of great significance to the development of short-wave ultraviolet lasers.As a structural analogy to BeO_(4),the ZnO_(4) unit has been demonstrated as a facile building unit for the design of beryllium-free borates with balanced overall performance.Nevertheless,despite the discovery of numerous zincoborates,no Sr_(2)Be_(2)B_(2)O_(7)-type zincoborates with characteristic bilayer structures constituted by ZnO_(4) and BO_(3) units have been found,highlighting the great challenge in the design and syntheses of Sr_(2)Be_(2)B_(2)O_(7)-type zincoborates.Herein,two new beryllium-free Sr_(2)Be_(2)B_(2)O_(7)-type zincoborates,namely,Na_(3)AEZn_(2)B_(3)O_(9)(AE=Mg and Ca),were rationally obtained by a chemical cosubstitution design strategy.With the cosubstitution of Sr^(2+),Be^(2+)and out-of-plane bridging O2−of{Sr[Be_(2)(BO_(3))_(2)O]}_(∞)^(2−)bilayers of Sr_(2)Be_(2)B_(2)O_(7),Na_(3)AEZn_(2)B_(3)O_(9)(AE=Mg and Ca)featuring a new Sr_(2)Be_(2)B_(2)O_(7)-type bilayer structure of{Na_(3)[Zn_(2)(BO_(3))_(2)(BO_(3))]}_(∞)^(2−) were successfully isolated,indicating the feasibility of chemical cosubstitution for the design of Sr_(2)Be_(2)B_(2)O_(7)-type zincoborates.In particular,Na_(3)CaZn_(2)B_(3)O_(9) exhibits a wide band gap of 4.43 eV,a moderate birefringence of 0.045@1064 nm and a high melting point of 843℃,being favorable to practical applications.展开更多
As a critical component of polarization devices and optical devices,birefringent crystals are widely used in high-tech fields such as laser communication,laser polarization engineering,and high-precision scientific re...As a critical component of polarization devices and optical devices,birefringent crystals are widely used in high-tech fields such as laser communication,laser polarization engineering,and high-precision scientific research instruments.In this study,two new hydroxyl borates,KB_(7)O_(9)(OH)_(4)and KB_(7)O_(10)(OH)_(2),were synthesized successfully via the hydrothermal method.The two hepta-borates feature different fundamental building units:[B_(7)O_(10)(OH)_(4)]in KB_(7)O_(9)(OH)_(4)and[B_(7)O_(12)(OH)_(2)]in KB_(7)O_(10)(OH)_(2).These units polymerize through oxygen atoms to form a one-dimensional(1D)infinite[B_(7)O_(10)(OH)_(4)]chain and a two-dimensional(2D)[B_(7)O_(12)(OH)_(2)]layer,respectively,demonstrating a hydroxyl-induced structural reconstruction.Notably,the 1D[B_(7)O_(9)(OH)_(4)]_(∞)infinite chain in KB_(7)O_(9)(OH)_(4)represents the first such structure identified in inorganic hydrated hepta-borates,as confirmed by the ICSD database.Performance characterization reveals that both compounds exhibit deep-UV transparency(with cut-off wavelengths shorter than 200 nm)and moderate birefringence values ranging from 0.041 to 0.078 at 546 nm,highlighting their potential as deep-UV birefringent crystal candidates.展开更多
As the first reported examples of borates in the Zn-Sc-B-O system,Ba_(2)ZnSc(BO_(3))_(3)and Ba_(4)Zn_(5)Sc_(2)(BO_(3))_(8)were synthesized through a high-temperature solution method.The structure of Ba_(2)ZnSc(BO_(3))...As the first reported examples of borates in the Zn-Sc-B-O system,Ba_(2)ZnSc(BO_(3))_(3)and Ba_(4)Zn_(5)Sc_(2)(BO_(3))_(8)were synthesized through a high-temperature solution method.The structure of Ba_(2)ZnSc(BO_(3))_(3)can be described as ZnO_(4)tetrahedra connecting ScO_(6)octahedra to form a[ZnScO_(9)]^(13-)dimer,which further bonds with seven BO_(3)triangles to form a_(∞)^(2)[ZnSc(BO_(3))_(3)]layer,and the Ba atoms distribute in the voids between the layers.In contrast,in Ba_(4)Zn_(5)Sc_(2)(BO_(3))_(8),Zn-O chains composed of 4-and 6-coordinated Zn atoms link with Sc_(2)O_(8)dimers to form a Zn-Sc-O layer,and the BO_(3)triangles and Ba atoms fill in the voids between the layers.Interestingly,the special[Zn_(2)(BO_(3))6]^(14-)cluster is found in Ba_(2)ZnSc(BO_(3))_(3),which is different from the 2D layers or 3D frameworks of the Zn-B-O configurations in other zincoborates.Moreover,the lowest-coordinated ScO5 polyhedra,as well as the coexistence of two types of ZnOn units(n=4 and 6),are observed for the first time in Ba_(4)Zn_(5)Sc_(2)(BO_(3))_(8).These fascinating results can promote the design of novel borates with BO_(3)units and enrich the borate structure chemistry.展开更多
Birefringence determined by optical anisotropy is one of the most pivotal and fundamental performance of optical materials.However,optimizing the birefringence remains a significant challenge.Herein,a simple and effec...Birefringence determined by optical anisotropy is one of the most pivotal and fundamental performance of optical materials.However,optimizing the birefringence remains a significant challenge.Herein,a simple and effective method of cation chemical substitution for improving the birefringence has been accomplished and three Y-based borates,namely,LiNa_(2)Y(BO_(3))_(2),RbNa_(2)Y(BO_(3))_(2)and RbSrY(BO_(3))_(2),were successfully synthesized.They all have deep-ultraviolet(DUV)cutoff edges below 190 nm.Single-crystal analysis reveals that LiNa_(2)Y(BO_(3))_(2)and RbNa_(2)Y(BO_(3))_(2)possess three-dimensional(3D)frameworks with small channels filled by alkali metal cations,whereas RbSrY(BO_(3))_(2)features a two-dimensional(2D)layered structure separated by alkali metal and alkali-earth metal cations.The birefringence exhibits a progressive doubling increase from LiNa_(2)Y(BO_(3))_(2)(0.017@532 nm)to RbNa_(2)Y(BO_(3))_(2)(0.033@532 nm)and then to RbSrY(BO_(3))_(2)(0.070@532 nm).Using cation size arguments,coordination environment,and the arrangement of groups demonstrate that cation substitution have a decisive effect on the birefringence enhancement.In addition,other optical and thermal properties of the three title compounds were characterized.The structure–property relationships were analyzed by the first-principles calculations.展开更多
The mixed-alkali-metal borates NaK(B_(5)O_(8))(OH)·H2O(1),NaK_(6)[(B_(4)O_(5))(OH)_(4)]3(OH)·C_(2)H_(5)OH(2)and Na_(0.33)K_(1.67)(B_(4)O_(5))(OH)_(4)·3H_(2)O(3)have been solvothermally synthesized using...The mixed-alkali-metal borates NaK(B_(5)O_(8))(OH)·H2O(1),NaK_(6)[(B_(4)O_(5))(OH)_(4)]3(OH)·C_(2)H_(5)OH(2)and Na_(0.33)K_(1.67)(B_(4)O_(5))(OH)_(4)·3H_(2)O(3)have been solvothermally synthesized using various polar organic solvents.Compounds 1 and 2 crystallize in the centrosymmetric space groups P1¯and R3¯c,respectively.展开更多
Main observation and conclusion A new Rh(Ⅲ)-catalyzed direct C—H alkenylation of 2,3-unsubstitued indoles with alkenyl borates through C—H activation followed by transmetallation was described.This protocol provide...Main observation and conclusion A new Rh(Ⅲ)-catalyzed direct C—H alkenylation of 2,3-unsubstitued indoles with alkenyl borates through C—H activation followed by transmetallation was described.This protocol provides an efficient method for the synthesis of terminal C2-alkenylindoles under mild conditions,and also shows broad substrate scope and high functional group tolerance with respect to both components.Furthermore,the C2-alkenylated indole can be easily transformed into carboline derivative,which is an important polycyclic indole moiety in natural products and drug molecules.展开更多
As a promising candidate,the fluorooxoborate has enkindled new explorations of nonlinear optical materials to meet the deep-ultraviolet criteria.However,big challenges and open questions still remain facing this excit...As a promising candidate,the fluorooxoborate has enkindled new explorations of nonlinear optical materials to meet the deep-ultraviolet criteria.However,big challenges and open questions still remain facing this exciting new field,especially the birefringence and dispersion of refractive index which are fundamental parameters for determining the phasematching second harmonic generation wavelength.Here we designed possible anionic groups in fluorooxoborates,and analyzed the optical anisotropy to check its influence on birefringence,which was proved further by the response electronic distribution anisotropy approximation.The functional modules modulating birefringence in fluorooxoborates were explored systematically.We developed an approach for evaluating the behavior of the refractive index dispersions and found that the fluorooxoborates had small refractive index dispersions owing to the introduction of fluorooxoborate modules.Our results demonstrate that fluorooxoborates can be utilized to realize short phase-matching wavelength markedly and offer a path toward novel performance-driven materials design.展开更多
As a fundamental parameter of the optical crystals,birefringence plays a vital role in many optical applications,such as phase modulation,light splitting,and polarization,especially the phase matching process of the n...As a fundamental parameter of the optical crystals,birefringence plays a vital role in many optical applications,such as phase modulation,light splitting,and polarization,especially the phase matching process of the nonlinear optical crystals.The big birefringence not only benefits to the miniaturization of related devices,but also broadens the phase-matching wavelength range of nonlinear optical crystals.The design and synthesis of crystals with large birefringence becomes a hot research topic due to its more and more important applications in the optical modulation and laser technology fields.Herein,crystals with birefringence greater than 0.05 in the borate system are reviewed and classified according to different birefringent active groups,and the relationship between structure and properties is thoroughly explored.It is hoped that this review will provide a clear understanding of what kinds of building units and arrangements would have more opportunity to get adequate birefringence in borate systems and provide the statistical references to encourage the emergence of better crystal materials with large birefringence.展开更多
Aluminoborates(ABOs)show wide ultraviolet(UV)transmittance,and are one of the important types of UV and deep-UV nonlinear optical(NLO)materials.In recent years,the combination of AlO_(n)(n=4,5,6)polyhedra or their flu...Aluminoborates(ABOs)show wide ultraviolet(UV)transmittance,and are one of the important types of UV and deep-UV nonlinear optical(NLO)materials.In recent years,the combination of AlO_(n)(n=4,5,6)polyhedra or their fluorinated analogues with different polyborate anions leads to a rich variety of crystalline ABOs.In this review,we summarize the recent developments of UV and deep-UV NLO inorganic ABOs.These ABOs can be grouped into three types in terms of their compositions:(i)aluminum oxyborates,(ii)alkali/alkaline earth metal aluminoborates,and(iii)alkali/alkaline earth metal aluminoborate fluorides and fluoroaluminoborates.We discuss the synthesis,structural features,NLO properties,as well as related structure-performance relationships of these non-centrosymmetric ABOs.Finally,the future perspectives in this field are discussed.展开更多
基金supported by the National Natural Science Foundation of China(No.22171046)the Hundred-Talent Project of Fujian(No.50021113)Fuzhou University(No.0480-00489503)。
文摘In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.There are rare examples where the 9-BBN derivatives serve as the potentially diverse C8 building blocks in cross-coupling reactions.Herein,we report a cobalt-catalyzed migratory carboncarbon cross-coupling reaction of the in situ formed 9-BBN ate complexes to afford diverse aryl-and alkyl-functionalized cyclooctenes.Preliminary mechanistic studies suggest the oxidation-induced cisbicyclo[3.3.0]oct-1-ylborane is the key intermediate in this migratory cross-coupling reaction,which promotes the development of other diverse migratory cross-coupling of borate complexes.
基金supported by the National Natural Science Foundation of China(Grant No.52403305)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0880000)+1 种基金Tianchi Talent Program of Xinjiang Uygur Autonomous Region(Grant No.2024000068)Postdoctoral Fellow-ship Program(Grade C)(Grant No.GZC20232959)。
文摘The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic frameworks formed by B–O and B–O–F units significantly determine the physical properties of fluorooxoborates.Therefore,the rational design of anionic frameworks could facilitate the materials discovery process.Herein,we propose that a candidate anionic framework can be efficiently derived from an existing one by slightly altering its oxygen content.Following this idea,we hypothesized the existence of a 1D[B_(3)O_(5)F]_(∞)chain from the wellknown 2D[B_(6)O_(9)F_(2_)]_(∞)layer.Accordingly,seven CaB_(3)O_(5)F structures with the expected anionic framework were successfully predicted.First-principles calculations show that all these structures have potential in the UV/DUV birefringent or nonlinear optical(NLO)material field,indicating that the 1D[B_(3)O_(5)F]_(∞)chain is indeed a promising anionic framework for achieving UV/DUV birefringent and NLO performance.
基金supported by the National Natural Science Foundation of China(No.50972149,61138004,51402316)the National Instrumentation Program(No.2012YQ120048)
文摘Two new isostructural multi-metal beryllium borates, m^3 Li Na4Be4B10O24F（M = Sr（1）, Cd（2））, have been synthesized by spontaneous crystallization. The structures were verified by single-crystal X-ray crystallography. The compounds crystallize in the trigonal space group R 3, with a = b = 9.4645（1） A, c = 38.842（8） A, V = 3013.2（6） A3, Z = 6, F（000） = 2568, Dc = 3.005 g/cm^3, Mr = 908.9, R = 0.0327, w R = 0.0678, μ = 8.160 mm-1 for Sr3 Li Na4Be4B10O24F and a = b = 9.3019（8） A, c = 37.782（7） A, V = 2831.12（9） A3, Z = 6, F（000） = 2748, Dc = 3.459 g/cm^3, Mr = 983.24, R = 0.0158, w R = 0.0455, μ = 3.586 mm-1 for Cd3 Li Na4Be4B10O24F. The structures are characterized by an infinite two-dimensional [Be8B16O40F2]∞ double layer bridged by [B12O24] groups like a sandwich structure, while the cations reside in tunnels along different directions. UV-vis-IR diffuse reflectance spectroscopy demonstrates that their cut-off edges are below 200 nm. Thermal analysis shows that they melt incongruently and their melting points are around 740-770 ℃.
基金supported in part by the Russian Foundation for Basic Research (07-02-01185)the Russian Academy of Sciences under thgrams for Basic Research
文摘This paper is devoted to the rare-earth borates described by the general formula RM3（BO3）4, M = Al, Fe, and Cr, that have non-centrosymmetric trigonal slructure of the natural mineral huntite. It give a brief review of a spectroscopic research on YbAI3（BO3）4 （YbAB）, on a large group of magnetic iron borates, and on NdCra（BO3）4.
基金Financial supports from the NNSFCs (Grants 21276194 and 21306136)the Specialized Research Fund for the Doctoral Program of Chinese Higher Education (Grant 20101208110003)the Opening Funds of Tianjin Key Laboratory of Marine Resources and Chemistry for Tianjin University of Science and Technology (Grant 201206)
文摘1 Introduction Lithium and its compounds as national strategic resources are extensively used in national defense,industrial and agricultural production.As we know,the salt lakes in the western of China are famous for its high
基金Financial support from the State Surface Project of National Natural Science of China (21276194)the Specialized Research Fund for the Doctoral Program of Chinese Higher Education (20101208110003)the Key Pillar Program of Tianjin Municipal Science and Technology (11ZCKGX02800)
文摘Amounts of lithium-containing salt lake brine resources are widely distributed in the four provinces named Qinghai,Tibet,Inner Mongolia and Xinjiang province,especially the salt lakes in Qinghai-Tibet Plateau are abundant of
基金Financial supports from the NNSFCs (Grants 201276194 and 201306136)the Funds of Tianjin Key Laboratory of Marine Resources and Chemistry in TUST (Grants 201303 and 201206)the Natural Science Fund of TUST (Grant 20130112)
文摘It is well known that boron exists as polyborate anions in aqueous solution.Boron atom can coordinates to three or four oxygen atoms and borate can exist as not only the monomer but also the polymer.The polymerization
基金supported by the Natural Science Foundation of Ningbo City (2007A610022) K. C. Wong Magna Fund in Ningbo University
文摘Two new nonmetal borates, [（C2H10N2）]2[B14O20（OH）6] 1 and [C8H22N4][B5O6（OH）4]2 2, have been synthesized under mild conditions and characterized by single-crystal X-ray diffraction, FTIR, elemental analysis and thermogravimetric analysis. Crystal data for compound 1： triclinic, space group P^-1, a = 8.4979（17）, b = 8.8498（18）, c = 10.065（2）A^°, α = 95.01（3）, β = 96.99（3）, γ = 116.82（3）°, V= 661.8（3）A^°^3, Z= 1, Mr = 697.63, Dc = 1.751 g/cm^3,μ = 0.163 mm^-1, F（000） = 356, the final R = 0.0372 and wR = 0.0968 （I 〉 2σ（I））; and those for compound 2： monoclinic, space group P21/c, a = 9.1867（18）, b= 14.118（3）, c = 10.334（2）A^°, β = 91.48（3）°, V = 1339.8（5）A^°^3, Z = 2, Mr = 610.46, Dc = 1.513 g/cm^3,μ = 0.135 mm^-1, F（000） = 632, the final R = 0.0350 and wR = 0.0912 （I 〉 2σ（I））. For both 1 and 2, the anionic units are interlinked via O-H…O hydrogen bonds to form a 3D supramolecular network, while the protonated cations are located in the free space of the inorganic borate framework and interact with the anions by electrostatic attraction and extensive N-H…O hydrogen bonds.
基金the National Natural Science Foundation of China (50275147)Program for New Century Excellent Talents in Chinese University (NCET-04-1002)Program for Innovative Groups in Chongqing’s Higher Schools
文摘The antiwear and friction-reducing performances of sodium borate, potassium borate and lanthanum chloride in water were evaluated on a four-ball friction tester. The topographies, element distribution and chemical characteristics of the worn surfaces were investigated by scanning electron microscope （SEM）, energy dispersion of X-ray （EDX） and X-ray photoelectron spectroscope （XPS）. The results indicated that sodium borate, potassium borate and lanthanum chloride increased extreme pressure, antiwear and friction-reducing capacities of water to a certain extent, of which potassium borate was the best candidate. Combination of lanthanum chloride with sodium borate and po- tassium borate respectively further improved antiwear and friction-reducing capacities. Scratches of worn surfaces lubricated with water containing borates and lanthanum chloride were less severe than those lubricated with water containing borates alone. A tribochemical film mainly composed of oxides of lanthanum, boron and iron reduced friction and wear for water lubricant formulated with both borates and lanthanum chloride.
文摘A benzotriazole-containing derivative was synthesized via the Mannich reaction.The structure was characterized by NMR spectroscopy.By utilizing computational chemistry and molecular simulation,the calculation and mapping of atomic charge and frontier molecular orbitals with complex structure of the borate were carried out.The acid number of BTBE(nitrogen-containing heterocyclic borate)was determined by the standard test method for acid number and the open observation method.The results showed that BTBE had a low initial acid number,because the acid number was changed only after 72 hours of hydrolysis,and it was negative after the hydrolysis reached 120 hours.The extreme-pressure friction resistance of BTBE and other four base oils was also determined.For 5 kinds of base oils,the friction experiment was carried out under a load of 30 kgf,and the BTBE showed a lowest wear scar diameter(0.365 mm)along with a highest maximum non-seizure load.The results showed that the EP friction resistance of BTBE was stronger than that of other four base oils under the same test conditions.The results of hydrolysis performance showed that the synthesized nitrogencontaining heterocyclic borate had a high resistance to hydrolysis,while demonstrating broad application prospects.
基金the Natural Science Foundation of Henan Province (0611021600, 0311050500)the Key Discipline Foundation of Zhoukou Normal University
文摘Two new borate compounds, C4H10N2·B6O8（OH）2 and （NH3CH2CH2NH3）B5O8 （OH）2, have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, elemental analysis and thermal analysis. Compound 1 crystallizes in the monoclinic system, space group P21/c, with a = 8.3318（17）, b = 6.2118（12）, c = 12.479（3） A, β = 108.96（3）°, V = 610.8（2） A^3, Mr = 313.02, Z = 2, 13,.= 1.702 g/cm^,/J = 0.150 mm^-1, F（000） = 320, R = 0.0387 and wR = 0.0924. Its layered structure is linked by infinite covalently coordinated neutral sheets with 3,20-membered window system, which are built up from alternative B6O8（OH）2 subunits donated by two piperzazine nitrogen donors. 2 crystallizes in monoclinic, space group Co, with a = 6.7207（13）, b = 11.481 （2）, c = 12.564（3）A,β = 95.25（3）°, V = 965.4（3） A^3, Mr = 261.18, Z = 4, Dc = 1.797 g/cm^3,/t = 0.164 mm^-1, F（000） = 536, R = 0.0396 and wR = 0.0752. Its oxoborate structure is generated from the sheets of 3,9-membered boron rings bonded diamine molecules through electrostatic and H-bonding interactions to form a two-dimensional layered network.
基金supported by the National Natural Science Foundation of China(No.22031009,21875248,and 91963105).
文摘Exploration of short-wave ultraviolet beryllium-free Sr_(2)Be_(2)B_(2)O_(7)-type borates is of great significance to the development of short-wave ultraviolet lasers.As a structural analogy to BeO_(4),the ZnO_(4) unit has been demonstrated as a facile building unit for the design of beryllium-free borates with balanced overall performance.Nevertheless,despite the discovery of numerous zincoborates,no Sr_(2)Be_(2)B_(2)O_(7)-type zincoborates with characteristic bilayer structures constituted by ZnO_(4) and BO_(3) units have been found,highlighting the great challenge in the design and syntheses of Sr_(2)Be_(2)B_(2)O_(7)-type zincoborates.Herein,two new beryllium-free Sr_(2)Be_(2)B_(2)O_(7)-type zincoborates,namely,Na_(3)AEZn_(2)B_(3)O_(9)(AE=Mg and Ca),were rationally obtained by a chemical cosubstitution design strategy.With the cosubstitution of Sr^(2+),Be^(2+)and out-of-plane bridging O2−of{Sr[Be_(2)(BO_(3))_(2)O]}_(∞)^(2−)bilayers of Sr_(2)Be_(2)B_(2)O_(7),Na_(3)AEZn_(2)B_(3)O_(9)(AE=Mg and Ca)featuring a new Sr_(2)Be_(2)B_(2)O_(7)-type bilayer structure of{Na_(3)[Zn_(2)(BO_(3))_(2)(BO_(3))]}_(∞)^(2−) were successfully isolated,indicating the feasibility of chemical cosubstitution for the design of Sr_(2)Be_(2)B_(2)O_(7)-type zincoborates.In particular,Na_(3)CaZn_(2)B_(3)O_(9) exhibits a wide band gap of 4.43 eV,a moderate birefringence of 0.045@1064 nm and a high melting point of 843℃,being favorable to practical applications.
基金supported by the National Natural Science Foundation of China(22361132544,22193044,and 22335007)the Tianshan Basic Research Talents Program(2022TSYCJU0001)+2 种基金the CAS Project for Young Scientists in Basic Research(YSBR-024)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0880000)the Xinjiang Tianchi Talents Program.ARO’s work was supported by the Russian Science Foundation(grant 24-43-00162).
文摘As a critical component of polarization devices and optical devices,birefringent crystals are widely used in high-tech fields such as laser communication,laser polarization engineering,and high-precision scientific research instruments.In this study,two new hydroxyl borates,KB_(7)O_(9)(OH)_(4)and KB_(7)O_(10)(OH)_(2),were synthesized successfully via the hydrothermal method.The two hepta-borates feature different fundamental building units:[B_(7)O_(10)(OH)_(4)]in KB_(7)O_(9)(OH)_(4)and[B_(7)O_(12)(OH)_(2)]in KB_(7)O_(10)(OH)_(2).These units polymerize through oxygen atoms to form a one-dimensional(1D)infinite[B_(7)O_(10)(OH)_(4)]chain and a two-dimensional(2D)[B_(7)O_(12)(OH)_(2)]layer,respectively,demonstrating a hydroxyl-induced structural reconstruction.Notably,the 1D[B_(7)O_(9)(OH)_(4)]_(∞)infinite chain in KB_(7)O_(9)(OH)_(4)represents the first such structure identified in inorganic hydrated hepta-borates,as confirmed by the ICSD database.Performance characterization reveals that both compounds exhibit deep-UV transparency(with cut-off wavelengths shorter than 200 nm)and moderate birefringence values ranging from 0.041 to 0.078 at 546 nm,highlighting their potential as deep-UV birefringent crystal candidates.
基金supported by the National Natural Science Foundation of China(Grant No.21501194,51425206,91622107)National Basic Research Program of China(Grant No.2014CB648400)+5 种基金Xinjiang International Science&Technology Cooperation Program(20166009)the Xinjiang Program of Cultivation of Young Innovative Technical Talents(QN2016JQ0395)the National Key Research Project(Grant No.2016YFB1102302,2016YFB0402104)Xinjiang Key Research and Development Program(Grant No.2016B02021)Major Program of Xinjiang Uygur Autonomous Region of China during the 13th Five-Year Plan Period(Grant No.2016A02003)West Light Foundation of the Chinese Academy of Sciences(Grant No.2016-YJRC-2).
文摘As the first reported examples of borates in the Zn-Sc-B-O system,Ba_(2)ZnSc(BO_(3))_(3)and Ba_(4)Zn_(5)Sc_(2)(BO_(3))_(8)were synthesized through a high-temperature solution method.The structure of Ba_(2)ZnSc(BO_(3))_(3)can be described as ZnO_(4)tetrahedra connecting ScO_(6)octahedra to form a[ZnScO_(9)]^(13-)dimer,which further bonds with seven BO_(3)triangles to form a_(∞)^(2)[ZnSc(BO_(3))_(3)]layer,and the Ba atoms distribute in the voids between the layers.In contrast,in Ba_(4)Zn_(5)Sc_(2)(BO_(3))_(8),Zn-O chains composed of 4-and 6-coordinated Zn atoms link with Sc_(2)O_(8)dimers to form a Zn-Sc-O layer,and the BO_(3)triangles and Ba atoms fill in the voids between the layers.Interestingly,the special[Zn_(2)(BO_(3))6]^(14-)cluster is found in Ba_(2)ZnSc(BO_(3))_(3),which is different from the 2D layers or 3D frameworks of the Zn-B-O configurations in other zincoborates.Moreover,the lowest-coordinated ScO5 polyhedra,as well as the coexistence of two types of ZnOn units(n=4 and 6),are observed for the first time in Ba_(4)Zn_(5)Sc_(2)(BO_(3))_(8).These fascinating results can promote the design of novel borates with BO_(3)units and enrich the borate structure chemistry.
基金supported by the National Natural Science Foundation of China(Grant No.52322202 and 22071179)Natural Science Foundation of Tianjin(Grant No.20JCJQJC00060 and 21JCJQJC00090).
文摘Birefringence determined by optical anisotropy is one of the most pivotal and fundamental performance of optical materials.However,optimizing the birefringence remains a significant challenge.Herein,a simple and effective method of cation chemical substitution for improving the birefringence has been accomplished and three Y-based borates,namely,LiNa_(2)Y(BO_(3))_(2),RbNa_(2)Y(BO_(3))_(2)and RbSrY(BO_(3))_(2),were successfully synthesized.They all have deep-ultraviolet(DUV)cutoff edges below 190 nm.Single-crystal analysis reveals that LiNa_(2)Y(BO_(3))_(2)and RbNa_(2)Y(BO_(3))_(2)possess three-dimensional(3D)frameworks with small channels filled by alkali metal cations,whereas RbSrY(BO_(3))_(2)features a two-dimensional(2D)layered structure separated by alkali metal and alkali-earth metal cations.The birefringence exhibits a progressive doubling increase from LiNa_(2)Y(BO_(3))_(2)(0.017@532 nm)to RbNa_(2)Y(BO_(3))_(2)(0.033@532 nm)and then to RbSrY(BO_(3))_(2)(0.070@532 nm).Using cation size arguments,coordination environment,and the arrangement of groups demonstrate that cation substitution have a decisive effect on the birefringence enhancement.In addition,other optical and thermal properties of the three title compounds were characterized.The structure–property relationships were analyzed by the first-principles calculations.
基金financially supported by the National Natural Science Foundation of China(no.51432006,50925207,and 51172100)the Ministry of Science and Technology of China(no.2011DFG52970)+1 种基金the Ministry of Education of China for the Changjiang Innovation Research Team(no.IRT13R24)the Ministry of Education and the State Administration of Foreign Experts Affairs for the 111 Project(no.B13025).M.G.H.and C.Z.thank the Australian Research Council for support.
文摘The mixed-alkali-metal borates NaK(B_(5)O_(8))(OH)·H2O(1),NaK_(6)[(B_(4)O_(5))(OH)_(4)]3(OH)·C_(2)H_(5)OH(2)and Na_(0.33)K_(1.67)(B_(4)O_(5))(OH)_(4)·3H_(2)O(3)have been solvothermally synthesized using various polar organic solvents.Compounds 1 and 2 crystallize in the centrosymmetric space groups P1¯and R3¯c,respectively.
基金We are grateful to the National Natural Science Foundation of China(No.21302064)the Natural Science Foundation of Hubei Province(No.2017CFB690).
文摘Main observation and conclusion A new Rh(Ⅲ)-catalyzed direct C—H alkenylation of 2,3-unsubstitued indoles with alkenyl borates through C—H activation followed by transmetallation was described.This protocol provides an efficient method for the synthesis of terminal C2-alkenylindoles under mild conditions,and also shows broad substrate scope and high functional group tolerance with respect to both components.Furthermore,the C2-alkenylated indole can be easily transformed into carboline derivative,which is an important polycyclic indole moiety in natural products and drug molecules.
基金supported by the National Natural Science Foundation of China(51922014,11774414,51972336 and 61835014)the Key Research Program of Frontier Sciences,CAS(ZDBSLY-SLH035)+2 种基金Tianshan Innovation Team Program(2018D14001)the Western Light Foundation of CAS(Y92S191301)Fujian Institute of Innovation,CAS。
文摘As a promising candidate,the fluorooxoborate has enkindled new explorations of nonlinear optical materials to meet the deep-ultraviolet criteria.However,big challenges and open questions still remain facing this exciting new field,especially the birefringence and dispersion of refractive index which are fundamental parameters for determining the phasematching second harmonic generation wavelength.Here we designed possible anionic groups in fluorooxoborates,and analyzed the optical anisotropy to check its influence on birefringence,which was proved further by the response electronic distribution anisotropy approximation.The functional modules modulating birefringence in fluorooxoborates were explored systematically.We developed an approach for evaluating the behavior of the refractive index dispersions and found that the fluorooxoborates had small refractive index dispersions owing to the introduction of fluorooxoborate modules.Our results demonstrate that fluorooxoborates can be utilized to realize short phase-matching wavelength markedly and offer a path toward novel performance-driven materials design.
基金supported by Shanghai Cooperation Organization Science and Technology Partnership Program(2020E01039)the Scientific Instrument Developing Project,CAS(YJKYYQ20210033)+3 种基金CAS Youth Interdisciplinary Team(JCTD-2021–18)the West Light Foundation of CAS(2021-XBQNXZ-004)the Outstanding Youth Science Fund Project of Natural Science Foundation of Xinjiang(2022D01E90)Key Training Object of Talent Project of Urumqi。
文摘As a fundamental parameter of the optical crystals,birefringence plays a vital role in many optical applications,such as phase modulation,light splitting,and polarization,especially the phase matching process of the nonlinear optical crystals.The big birefringence not only benefits to the miniaturization of related devices,but also broadens the phase-matching wavelength range of nonlinear optical crystals.The design and synthesis of crystals with large birefringence becomes a hot research topic due to its more and more important applications in the optical modulation and laser technology fields.Herein,crystals with birefringence greater than 0.05 in the borate system are reviewed and classified according to different birefringent active groups,and the relationship between structure and properties is thoroughly explored.It is hoped that this review will provide a clear understanding of what kinds of building units and arrangements would have more opportunity to get adequate birefringence in borate systems and provide the statistical references to encourage the emergence of better crystal materials with large birefringence.
基金supported by the National Natural Science Foundation of China(Grant 21975224).
文摘Aluminoborates(ABOs)show wide ultraviolet(UV)transmittance,and are one of the important types of UV and deep-UV nonlinear optical(NLO)materials.In recent years,the combination of AlO_(n)(n=4,5,6)polyhedra or their fluorinated analogues with different polyborate anions leads to a rich variety of crystalline ABOs.In this review,we summarize the recent developments of UV and deep-UV NLO inorganic ABOs.These ABOs can be grouped into three types in terms of their compositions:(i)aluminum oxyborates,(ii)alkali/alkaline earth metal aluminoborates,and(iii)alkali/alkaline earth metal aluminoborate fluorides and fluoroaluminoborates.We discuss the synthesis,structural features,NLO properties,as well as related structure-performance relationships of these non-centrosymmetric ABOs.Finally,the future perspectives in this field are discussed.
