Three new complex borate compounds K7CaBi2B15O30, K7CaLa2B15 O30 and K7BaBi2B15O30 have been synthesized by the high-temperature solution method.K7CaLa2B15O30and K7CaBi2B15O30crystallize in the chiral trigonal space g...Three new complex borate compounds K7CaBi2B15O30, K7CaLa2B15 O30 and K7BaBi2B15O30 have been synthesized by the high-temperature solution method.K7CaLa2B15O30and K7CaBi2B15O30crystallize in the chiral trigonal space group R32, while K7BaBi2B15O30 crystallizes in the noncentrosymmetric orthorhombic polar space group Pca21. All of the title compounds have similar three-dimensional crystal structures, which are composed of isolated B5 O10 groups and LaO6 or BiO6 octahedra, and K^+, Ca^2+, and Ba^2+ cations fill into the cavities to keep charge balance. Based on our research, in the system of K7 MIIRE2 B15O30(MII= Ca, Sr,Ba, Zn, Cd, Pb, K/RE0.5;RE = Sc, Y, La, Gd, Lu, Bi),K7BaBi2B15O30 is unique and crystallizes in a different space group, which enriches the structural chemistry of borate.Detailed structural analyses indicate that the structural variation is due to the difference in size and coordination number of the alkaline-earth metal cations. Besides, UV-Vis-NIR spectroscopy analysis and the second-harmonic generation(SHG) measurement on the powder samples show that K7CaBi2B15O30 exhibits a UV cutoff edge(about 282 nm) and a moderate SHG response(about 0.6 × KDP). In addition,thermal analysis and infrared spectroscopy were also presented. To better understand the structure-property relationships of the title compounds, the first-principles calculations have been performed.展开更多
A novel ternary borate, sodium strontium pentaborate, NaSrB5O9, has been prepared by solid-state reaction below 800 ℃. The single-crystal X-ray structural analysis showed that NaSrB5O9 crystallizes in monoclinic, spa...A novel ternary borate, sodium strontium pentaborate, NaSrB5O9, has been prepared by solid-state reaction below 800 ℃. The single-crystal X-ray structural analysis showed that NaSrB5O9 crystallizes in monoclinic, space group P21/c with a = 6.499（2）, b = 13.979（3）, c = 8.045（2）A, β = 106.92（2）°, V = 699.2（3）A^3, Z = 4, Mr = 308.66, Dc = 2.932 g/cm^3, μ = 7.804 mm^-1, F（000） = 584, R = 0.0264 and wR = 0.0621 for 2426 observed reflections and 146 variables. NaSrB5O9 is a layered compound containing double ring B5O11 building units composed of two BO4 tetrahedra and three BO3 triangles. Each B5O11 unit is connected to four other equivalent units through exocyclic oxygen atoms to form a two-dimensional ∞^2 [B5O9]^3- layer. Symmetry-center related layers are stacked along the b axis and held together by Na^＋ and Sr^2＋ cations via electrostatic interactions.展开更多
A new pentaborate, KNa2CdB5O（10）, has been synthesized and its crystal structure was determined by single-crystal XRD method with the following crystal data： KNa2CdB5O（10）, Pccn, a = 18.4555（13）, b = 8.3040（10...A new pentaborate, KNa2CdB5O（10）, has been synthesized and its crystal structure was determined by single-crystal XRD method with the following crystal data： KNa2CdB5O（10）, Pccn, a = 18.4555（13）, b = 8.3040（10）, c = 12.8772（9） A, V = 1973.5（3） A3, Z = 8, Mr = 411.53, Dc= 2.770 g/cm3, μ = 2.765 mm（-1）, F（000） = 1552, R = 0.0648 and w R = 0.1756 for 1684 observed reflections and 175 variables. It contains the double ring [B5O（10）]（5-） groups composed of one BO4 tetrahedron and four BO3 triangles that are bridged by tetrahedral Cd（2＋） centers via common O atoms to form 2D [CdB5O（10）]n（3n-） layers, with A＋（A = K/Na, Na） cations situated between and within the layers. IR spectrum confirms the existence of BO3 and BO4 groups. UV-VIS diffuse reflectance spectrum shows a band gap of about 3.44 eV and solid-state fluorescence spectrum exhibits a broad emission band at around 386 nm. Band structure calculations indicate that KNa2CdB5O（10） is an indirect band-gap insulator, with the calculated energy gap（3.68 eV） close to the experimental one.展开更多
Cd-rich portion of the pseudo-binary system Cd3B2O6-Zn3B2O6 was investigated. A new cadmium zinc borate, Cd2.42Zn0.58B2O6, was synthesized successfully by a traditional solid-state reaction method. The compound crysta...Cd-rich portion of the pseudo-binary system Cd3B2O6-Zn3B2O6 was investigated. A new cadmium zinc borate, Cd2.42Zn0.58B2O6, was synthesized successfully by a traditional solid-state reaction method. The compound crystallizes in the monoclinic space group C2/c with a = 17.3048, b = 8.4356, c = 10.2962 A^°, β = 93.157°, V = 1500.7（2） A^°3, Dc = 5.683 g/cm^3, F（000） = 2301, Z = 24, R = 0.0351 and wR = 0.0741. In its structure, BO3 triangle, CdO6 and CdO5 （or ZnO5） polyhedra are joined together by sharing bridging O atoms to form an intricate three-dimensional framework. A comparison of the structures of Cd2.42Zn0.58B2O6, α-Cd3B2O6 and β-Cd3B2O6 is presented. The IR spectrum confirms the presence of BO3 unit. The UV cut-off wavelength of Cd2.42Zn0.58B2O6 is 313 nm. The differential thermal analysis （DTA） suggests that Cd2.42Zn0.58B2O6 is an incongruent melting compound.展开更多
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
A novel inorganic-organic hybrid borate,[Al2（fum）（H3BO3）（OH） 4]n·n（H3BO3） （1,H2fum = fumaric acid） ,has been synthesized and characterized by single-crystal X-ray diffraction,FTIR and elemental analysis...A novel inorganic-organic hybrid borate,[Al2（fum）（H3BO3）（OH） 4]n·n（H3BO3） （1,H2fum = fumaric acid） ,has been synthesized and characterized by single-crystal X-ray diffraction,FTIR and elemental analysis. Crystal data for compound 1： orthorhombic,space group Pnma,a = 14.108（3） ,b = 6.9412（14） ,c = 14.995（3）A,V = 1468.3（5）A^3,Z = 4,Mr = 359.72,Dc = 1.627 g/cm^3,μ = 0.254 mm^-1,F（000） = 736,the final R = 0.0492 and wR = 0.1650 with I 〉 2σ（I） . In compound 1,each Al^Ⅲ ion is coordinated by six oxygen atoms to adopt a distorted octahedral geometry. Both fumarate anion and the coordinated boric acid act as bidentate bridging ligands to link two neighboring Al^Ⅲ centers simultaneously. Each Al^Ⅲ ion is bridged by two μ2-hydroxyl ligands to construct an infinite wave-like [Al2（fum）（H3BO3）（OH） 4]n chain. These one-dimensional chains form hydrogen bonds with free boric acid molecules giving rise to a three-dimensional supramolecular network.展开更多
The title compound (H3NCH2CH2NH3)4[(VO)6(B10O22)2]·(H3O)7 1 has been synthe- sized by the hydrothermal method and determined by X-ray crystallography. Crystallographic data: monoclinic, space group C2/c, a = 20.2...The title compound (H3NCH2CH2NH3)4[(VO)6(B10O22)2]·(H3O)7 1 has been synthe- sized by the hydrothermal method and determined by X-ray crystallography. Crystallographic data: monoclinic, space group C2/c, a = 20.250(4), b = 13.448(3), c = 21.655(4) ?, β = 97.05(3)°, Mr = 851.74 (C4H30.5B10N4O28.5V3), V = 5852(2) ?3, Z = 8, Dc = 1.933 g/cm3, μ = 1.057 mm-1, F(000) = 3436, R = 0.0500 and wR = 0.1442 for 4511 observed reflections with I > 2σ(I). The structure con- sists of [(VO)6(B10O22)2]15- cluster anions that have a central band of six trans-edge-sharing VO5 square pyramids capped by two [B10O22]14- polyborate ligands. Other characterizations are also describ- ed by elemental analysis, IR spectrum and thermal analysis.展开更多
A new hydrated lithium borate, Li4[B8O13（OH）2]·3H2O, has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, FT-IR spectroscopy, simultaneous TGA-DTA and chemical analysis. It...A new hydrated lithium borate, Li4[B8O13（OH）2]·3H2O, has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, FT-IR spectroscopy, simultaneous TGA-DTA and chemical analysis. It crystal- lizes in the triclinic, space group P]-, a=8.4578（5） A, b=8.7877（5） A, c= 10.8058（7） A, a=87.740（3）°, β= 71.819（3）°, γ=61.569（3）°, Z=2, V=665.26（7） A3, Dc=2.043 g/cm3. Its crystal structure features polyborate ani- onic layers with the larger odd 13-membered boron rings constructed by [B8O13（OH）2]4- FBBs. Through designing the thermochemical cycle, the standard molar enthalpy of formation of this borate was determined to be -（7953.8 ± 6.6） kJ·mol-1 by using a heat conduction microcalorimeter.展开更多
基金supported by the West Light Foundation of the CAS(2016-YJRC-2 and 2015 XBQN-B-11)the National Natural Science Foundation of China(51602341 and 91622107)+2 种基金the Natural Science Foundation of Xinjiang(2016D01B061)Tianshan Innovation Team Program(2018D14001)Key research project of Frontier Science of CAS(QYZDB-SSW-JSC049)
文摘Three new complex borate compounds K7CaBi2B15O30, K7CaLa2B15 O30 and K7BaBi2B15O30 have been synthesized by the high-temperature solution method.K7CaLa2B15O30and K7CaBi2B15O30crystallize in the chiral trigonal space group R32, while K7BaBi2B15O30 crystallizes in the noncentrosymmetric orthorhombic polar space group Pca21. All of the title compounds have similar three-dimensional crystal structures, which are composed of isolated B5 O10 groups and LaO6 or BiO6 octahedra, and K^+, Ca^2+, and Ba^2+ cations fill into the cavities to keep charge balance. Based on our research, in the system of K7 MIIRE2 B15O30(MII= Ca, Sr,Ba, Zn, Cd, Pb, K/RE0.5;RE = Sc, Y, La, Gd, Lu, Bi),K7BaBi2B15O30 is unique and crystallizes in a different space group, which enriches the structural chemistry of borate.Detailed structural analyses indicate that the structural variation is due to the difference in size and coordination number of the alkaline-earth metal cations. Besides, UV-Vis-NIR spectroscopy analysis and the second-harmonic generation(SHG) measurement on the powder samples show that K7CaBi2B15O30 exhibits a UV cutoff edge(about 282 nm) and a moderate SHG response(about 0.6 × KDP). In addition,thermal analysis and infrared spectroscopy were also presented. To better understand the structure-property relationships of the title compounds, the first-principles calculations have been performed.
基金Supported by the Talent Training Funds of Beijing (20051D0501501)the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality, and the Natural Science Foundation of Beijing (No. 2073021)
文摘A novel ternary borate, sodium strontium pentaborate, NaSrB5O9, has been prepared by solid-state reaction below 800 ℃. The single-crystal X-ray structural analysis showed that NaSrB5O9 crystallizes in monoclinic, space group P21/c with a = 6.499（2）, b = 13.979（3）, c = 8.045（2）A, β = 106.92（2）°, V = 699.2（3）A^3, Z = 4, Mr = 308.66, Dc = 2.932 g/cm^3, μ = 7.804 mm^-1, F（000） = 584, R = 0.0264 and wR = 0.0621 for 2426 observed reflections and 146 variables. NaSrB5O9 is a layered compound containing double ring B5O11 building units composed of two BO4 tetrahedra and three BO3 triangles. Each B5O11 unit is connected to four other equivalent units through exocyclic oxygen atoms to form a two-dimensional ∞^2 [B5O9]^3- layer. Symmetry-center related layers are stacked along the b axis and held together by Na^＋ and Sr^2＋ cations via electrostatic interactions.
基金Supported by the National Natural Science Foundation of China(No.20871012)
文摘A new pentaborate, KNa2CdB5O（10）, has been synthesized and its crystal structure was determined by single-crystal XRD method with the following crystal data： KNa2CdB5O（10）, Pccn, a = 18.4555（13）, b = 8.3040（10）, c = 12.8772（9） A, V = 1973.5（3） A3, Z = 8, Mr = 411.53, Dc= 2.770 g/cm3, μ = 2.765 mm（-1）, F（000） = 1552, R = 0.0648 and w R = 0.1756 for 1684 observed reflections and 175 variables. It contains the double ring [B5O（10）]（5-） groups composed of one BO4 tetrahedron and four BO3 triangles that are bridged by tetrahedral Cd（2＋） centers via common O atoms to form 2D [CdB5O（10）]n（3n-） layers, with A＋（A = K/Na, Na） cations situated between and within the layers. IR spectrum confirms the existence of BO3 and BO4 groups. UV-VIS diffuse reflectance spectrum shows a band gap of about 3.44 eV and solid-state fluorescence spectrum exhibits a broad emission band at around 386 nm. Band structure calculations indicate that KNa2CdB5O（10） is an indirect band-gap insulator, with the calculated energy gap（3.68 eV） close to the experimental one.
基金supported by the Special Foundation for Young Scientists of Beijing(No.2014000020124G009)
文摘Cd-rich portion of the pseudo-binary system Cd3B2O6-Zn3B2O6 was investigated. A new cadmium zinc borate, Cd2.42Zn0.58B2O6, was synthesized successfully by a traditional solid-state reaction method. The compound crystallizes in the monoclinic space group C2/c with a = 17.3048, b = 8.4356, c = 10.2962 A^°, β = 93.157°, V = 1500.7（2） A^°3, Dc = 5.683 g/cm^3, F（000） = 2301, Z = 24, R = 0.0351 and wR = 0.0741. In its structure, BO3 triangle, CdO6 and CdO5 （or ZnO5） polyhedra are joined together by sharing bridging O atoms to form an intricate three-dimensional framework. A comparison of the structures of Cd2.42Zn0.58B2O6, α-Cd3B2O6 and β-Cd3B2O6 is presented. The IR spectrum confirms the presence of BO3 unit. The UV cut-off wavelength of Cd2.42Zn0.58B2O6 is 313 nm. The differential thermal analysis （DTA） suggests that Cd2.42Zn0.58B2O6 is an incongruent melting compound.
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supported by the Ningbo Natural Science Foundation (2009A610052)the "Qianjiang Talent" Programs of Zhejiang Province (2009R10032)the K. C. Wang Magna Fund in Ningbo University
文摘A novel inorganic-organic hybrid borate,[Al2（fum）（H3BO3）（OH） 4]n·n（H3BO3） （1,H2fum = fumaric acid） ,has been synthesized and characterized by single-crystal X-ray diffraction,FTIR and elemental analysis. Crystal data for compound 1： orthorhombic,space group Pnma,a = 14.108（3） ,b = 6.9412（14） ,c = 14.995（3）A,V = 1468.3（5）A^3,Z = 4,Mr = 359.72,Dc = 1.627 g/cm^3,μ = 0.254 mm^-1,F（000） = 736,the final R = 0.0492 and wR = 0.1650 with I 〉 2σ（I） . In compound 1,each Al^Ⅲ ion is coordinated by six oxygen atoms to adopt a distorted octahedral geometry. Both fumarate anion and the coordinated boric acid act as bidentate bridging ligands to link two neighboring Al^Ⅲ centers simultaneously. Each Al^Ⅲ ion is bridged by two μ2-hydroxyl ligands to construct an infinite wave-like [Al2（fum）（H3BO3）（OH） 4]n chain. These one-dimensional chains form hydrogen bonds with free boric acid molecules giving rise to a three-dimensional supramolecular network.
基金This work was supported by the Natural Science Foundation of Fujian Province (E0110013 and K02028)
文摘The title compound (H3NCH2CH2NH3)4[(VO)6(B10O22)2]·(H3O)7 1 has been synthe- sized by the hydrothermal method and determined by X-ray crystallography. Crystallographic data: monoclinic, space group C2/c, a = 20.250(4), b = 13.448(3), c = 21.655(4) ?, β = 97.05(3)°, Mr = 851.74 (C4H30.5B10N4O28.5V3), V = 5852(2) ?3, Z = 8, Dc = 1.933 g/cm3, μ = 1.057 mm-1, F(000) = 3436, R = 0.0500 and wR = 0.1442 for 4511 observed reflections with I > 2σ(I). The structure con- sists of [(VO)6(B10O22)2]15- cluster anions that have a central band of six trans-edge-sharing VO5 square pyramids capped by two [B10O22]14- polyborate ligands. Other characterizations are also describ- ed by elemental analysis, IR spectrum and thermal analysis.
文摘A new hydrated lithium borate, Li4[B8O13（OH）2]·3H2O, has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, FT-IR spectroscopy, simultaneous TGA-DTA and chemical analysis. It crystal- lizes in the triclinic, space group P]-, a=8.4578（5） A, b=8.7877（5） A, c= 10.8058（7） A, a=87.740（3）°, β= 71.819（3）°, γ=61.569（3）°, Z=2, V=665.26（7） A3, Dc=2.043 g/cm3. Its crystal structure features polyborate ani- onic layers with the larger odd 13-membered boron rings constructed by [B8O13（OH）2]4- FBBs. Through designing the thermochemical cycle, the standard molar enthalpy of formation of this borate was determined to be -（7953.8 ± 6.6） kJ·mol-1 by using a heat conduction microcalorimeter.
