The 2,2'-((sulfonylbis(4,1-phenylene))bis(oxy))diacetic acid(H2L) and 4,4'-bipyridine(4,4'-bipy) are employed as organic ligands to react with metal salts to obtain two new metal-organic frameworks(MOFs), ...The 2,2'-((sulfonylbis(4,1-phenylene))bis(oxy))diacetic acid(H2L) and 4,4'-bipyridine(4,4'-bipy) are employed as organic ligands to react with metal salts to obtain two new metal-organic frameworks(MOFs), namely [M2L2(4,4'-bipy)](M = Zn(1), Cu(2)). They have been successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction reveals that two complexes are isostructural and crystallize in orthorhombic system with space group Pbcn. All L^(2-) ligands bridge metal ions to form an infinite 1D Z-shaped chain along the a axis. Then through 4,4'-bipy, contiguous Z-shaped chains are linked to form a 2D layer structure. The luminescent studies of the H2L ligand and complex 1 in the solid state and thermogravimetric analyses(TGA) of two complexes are investigated.展开更多
Two new coordination polymers {[Zn2L1（2,2＇-bpy）2（H2O）2]·4H2O}n（1） and [Zn2L2（2,2＇-bpy）2（H2O）2]n（2）（H4L1 = terphenyl-2,2＇,4,4＇-tetracarboxylic acid, H4L2 = quarterphenyl-2,2＇,4,4＇-tetracarboxyli...Two new coordination polymers {[Zn2L1（2,2＇-bpy）2（H2O）2]·4H2O}n（1） and [Zn2L2（2,2＇-bpy）2（H2O）2]n（2）（H4L1 = terphenyl-2,2＇,4,4＇-tetracarboxylic acid, H4L2 = quarterphenyl-2,2＇,4,4＇-tetracarboxylic acid, and 2,2＇-bpy = 2,2＇-bipyridine） have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction studies. Complex 1 displays 2D wavelike networks, which are further joined together through O–H···O hydrogen bonds to give a 3D supramolecular network. Complex 2 exhibits 1D ladder-like chains, and they are further joined together by π-π stacking and O–H···O hydrogen bonding interactions to form a 3D supramolecular network. The results indicate that the backbone of carboxylate ligands has significant effects on the formation and structure of the resulting functional coordination polymers. Additionally, thermal stability and photoluminescent properties of 1 and 2 are also investigated in detail.展开更多
The single crystals and powder of a Yavapaiite Structure phosphate,namely,PbSb0.5Fe0.5（PO4）2,were synthesized by solid state method and characterized by X-ray single-crystal diffraction and powder diffraction.The ti...The single crystals and powder of a Yavapaiite Structure phosphate,namely,PbSb0.5Fe0.5（PO4）2,were synthesized by solid state method and characterized by X-ray single-crystal diffraction and powder diffraction.The title compound crystallizes in the monoclinic system,space group C2/c（No.15） with a = 16.716（4）,b = 5.186（7）,c = 8.130（2）A,β = 114.93（6）°,Z = 4,R（I 〉 2s（I）） = 0.0430,R indices（all data） = 0.0460,and T = 293（2） K.The title compound belongs to the Yavapaiite Structure A^（Ⅱ）M^（Ⅳ）（PO4）2 compounds,and the Sb1 atom and Fe1 atoms occupy the same site（M） and their occupancy factors are refined to be 0.5 and 0.5 having a sum occupancy factor of 1.0.Its structure consists of [M（PO）4]n^2n- layers running parallel to the（b,c） plane built up of cornerconnected MO6 octahedra and PO4 tetrahedra.Additionally,the calculations of energy band structure,and density of states have been performed with the density functional theory method.The studies of computational calculation and UV experimental results show that the new compound is an indirect band-gap insulator.展开更多
A new complex [Co（4,4＇-bpy）2（H2O）2（4-FBA）2]·（4,4＇-bpy）（1） has been hydro-thermally synthesized using cobalt,4,4＇-bipyridyl（4,4＇-bpy） and 4-fluorobenzoic acid（4-HFBA）,and characterized by thermal...A new complex [Co（4,4＇-bpy）2（H2O）2（4-FBA）2]·（4,4＇-bpy）（1） has been hydro-thermally synthesized using cobalt,4,4＇-bipyridyl（4,4＇-bpy） and 4-fluorobenzoic acid（4-HFBA）,and characterized by thermal analysis,single-crystal X-ray diffraction and magnetic property.The complex crystallizes in the triclinic system,space group P,Z = 1.Crystal data：C54H44CoF2N8O6,Mr = 997.90,a = 9.134（2）,b = 11.555（2）,c = 12.867（3） ,α = 66.02（3）,β = 77.96（3）,= 73.11（3）°,V = 1180.9（4） 3,Dc = 1.403 g/cm3,μ（MoKα） = 0.433 mm-1,F（000） = 517,the final R = 0.0633 and wR = 0.1171 for 2152 observed reflections（I 〉 2σ（I））.The title complex is assembled into 1D supramolecular chains parallel to [001] based on the adjacent molecular ··· stacking interactions and hydrogen bonds.The variable temperature magnetic measurements show a weak ferromagnetic behavior over 300-160 K followed by antiferromagnetic behavior below 160 K for the title complex.展开更多
A new uranium（Ⅵ）-polycarboxylate framework with honeycomb（6,3） nets {[Zn（phen）_2（H_2O）_2][（UO_2）_2（BDC）_3]·2H_2O}n（1, BDC = benzene-1,4-dicarboxylate） was hydrotherrmally synthesized by the reactio...A new uranium（Ⅵ）-polycarboxylate framework with honeycomb（6,3） nets {[Zn（phen）_2（H_2O）_2][（UO_2）_2（BDC）_3]·2H_2O}n（1, BDC = benzene-1,4-dicarboxylate） was hydrotherrmally synthesized by the reactions of Zn（NO_3）_2·6H_2O with phenanthroine, UO_2（NO_3）_2·6H_2O and benzene-1,4-dicarboxylate. The complex was structurally characterized by FT-IR spectroscopy, powder XRD and X-ray single-crystal diffraction. Crystal data for 1： monoclinic, space group Cc with M_r = 1522.19, a = 14.9385（10）, b = 20.4922（13）, c = 15.9728（10） ？, β = 100.1240（10）°, V = 4813.5（5） ？~3, Z = 4, D_c = 2.100 g？cm^（–3）, μ = 7.293 mm^（–1）, F（000） = 2872, the final R = 0.0224 and w R= 0.0677 for 6522 observed reflections with I 〉 2σ（I）. Hydrogen bonds and π-π stacking interactions contribute to the structural extension and stabilization. Experimental band gap of about 3.57 e V indicates its broad gap semiconductor nature. UV-Vis spectra and solid-state luminescence were discussed in detail. The compound exhibits photocatalytic activities for the degradation of rhodamine B.展开更多
β-LiZnPO4 single crystal was successfully synthesized via hydrothermal method.It crystallizes in the trigonal space group R3 with a = b = 13.6490 A, c = 9.1123 A, γ = 120.00° andZ = 18. Structure of the crystal...β-LiZnPO4 single crystal was successfully synthesized via hydrothermal method.It crystallizes in the trigonal space group R3 with a = b = 13.6490 A, c = 9.1123 A, γ = 120.00° andZ = 18. Structure of the crystal is constructed by LiO4, ZnO4 and PO4 tetrahedral units to form athree-dimensional （3D） framework. The crystal has a high transmission ranging from 350 to 800nm with UV cut-offedge at 220 nm. The nonlinear optical efficiency of the as-prepared β-LiZnPO4is about 1.2 times as large as that of KDP （KH2PO4） standard. Additionally, band structure anddensity of states calculations for β-LiZnPO4 were performed using the total-energy code CASTEEbased on density functional theory （DFT）.展开更多
The single crystal and crystallized powder of triphosphate CeP3O9 have been synthesized, and the space group of CeP3O9has been determined to be C2221 with the cell parameters ofa = 8.6059, b = 11.2437, c = 7.3518 A, V...The single crystal and crystallized powder of triphosphate CeP3O9 have been synthesized, and the space group of CeP3O9has been determined to be C2221 with the cell parameters ofa = 8.6059, b = 11.2437, c = 7.3518 A, V= 711.4（3） A^3, Z= 4, D,. = 3.520 g/cm^3, F（000） = 700, R = 0.0377 and wR = 0.0930. The absorption and emission spectra have been measured, for which the strongest absorption and emission peaks are located at 280 and 320 nm, respectively. The density of state （DOS） and dielectric function have been calculated by the DFT method. The crystal is transparent provided the wavelength is larger than 341 nm, and the observed ultraviolet cut-off edge is at about 350 nm for a polycrystalline power sample. It is possible that the triphosphate CeP3O9 will become an ultraviolet emission material.展开更多
A new molybdenum phosphate [Zn（Mo^v6P4O31H10）2（C4H144N3）2].2C4H13N3.8H2O 1 （C4H13N3 = diethylenetriamine） has been synthesized under hydrothermal condition. Single-crystal X-ray diffraction reveals that compound...A new molybdenum phosphate [Zn（Mo^v6P4O31H10）2（C4H144N3）2].2C4H13N3.8H2O 1 （C4H13N3 = diethylenetriamine） has been synthesized under hydrothermal condition. Single-crystal X-ray diffraction reveals that compound 1 crystallizes in the monoclinic, space group P21/n, a = 13.1679（3）, b = 22.1240（6）, c = 13.6146（3） A, β= 103.4847（7）°, V = 3856.95（16） A^3, C16H90N12O70P8ZnMo12, Mr = 3035.41, Z = 2, Dc = 2.614 g/cm^3, μ = 2.483 mm^-1, F（000） = 2968, S = 1.014, the final R = 0.0196 and wR = 0.0506 for 7486 observed reflections （1 〉 2σ（I））. Compound 1 consists of two identical rings of six edge-sharing MoOt, octahedra interconnected by one ZnO6 octahedron, whereas the PO4 tetrahedra which share their apices with the MoO6, octahedra are only located on one side of each Mo6, ring. The 2-charge of polyanion [Zn（Mo^v6P4O31H10）2]^2- unit is compensated in the crystal by two mono-protonated diethylenetriamines （C4H14N3）^＋. By hydrogen bonding interactions the polyanion of compound 1 is interconnected to form pseudo threedimensional molybdophosphate. Other characterizations by elemental analyses, IR spectrum and fluorescent spectrum are also described.展开更多
In recent years, motivated by the discovery of deep-UV（wavelengths below 200 nm） nonlinear optical（NLO） phosphates, Ba3P3O（10）X（Cl, Br）, phosphates have entered into a passionate research era. In this review, ...In recent years, motivated by the discovery of deep-UV（wavelengths below 200 nm） nonlinear optical（NLO） phosphates, Ba3P3O（10）X（Cl, Br）, phosphates have entered into a passionate research era. In this review, recently discovered phosphate materials containing different anionic groups, i.e., isolated [PO4], [P2O7] dimer, [P3O（10）] trimer, and [PO3]∞ chain, are summarized, including their syntheses, structures, NLO performances and properties. Especially phosphates with short absorption edges in the deep-UV region and good SHG efficiency are introduced in detail. We hope that this work will present a clear view of the crystal chemistry of phosphates and promote the discovery of new high-performing second-order NLO materials to meet the urgent needs in laser science.展开更多
Two ternary complexes Cu2A4[OP(OCH3)3]2 (A represents CH2=CH-COO- and CH2=C(CH3)-COO-) have been synthesized, and elemental analyses, IR, ESR, electronic reflectance spectra and magnetic studies were carried out. The ...Two ternary complexes Cu2A4[OP(OCH3)3]2 (A represents CH2=CH-COO- and CH2=C(CH3)-COO-) have been synthesized, and elemental analyses, IR, ESR, electronic reflectance spectra and magnetic studies were carried out. The single crystal X-ray diffraction shows that Cu2[CH2=C(CH3)-COO]4[OP(OCH3)3]2 is triclinic, with space group P1, a = 1.05128(13), b = 1.7559(5), c = 1.94479(3) nm, α =91.263(14)°,(β = 102.559(6)°,γ= 106.339(13)°, Z = 4 and R = 0.0668. Two copper(Ⅱ) atoms are bridged by four (a-methacrylate groups, and each copper(Ⅱ) atom is coordinated with a trimethyl phosphate molecule in the axial position, forming a distorted square pyramidal configuration. The symmetric center is between the two copper(Ⅱ) atoms, and the Cu-Cu bond distance is 0.26098(6) nm. The Cu-Cu distance and magnetic studies suggest that there exist anti-ferromagnetic interactions between the two copper(Ⅱ) atoms.展开更多
基金supported by the Natural Science Foundation of Zhejiang Province(No.Y12B010003)。
文摘The 2,2'-((sulfonylbis(4,1-phenylene))bis(oxy))diacetic acid(H2L) and 4,4'-bipyridine(4,4'-bipy) are employed as organic ligands to react with metal salts to obtain two new metal-organic frameworks(MOFs), namely [M2L2(4,4'-bipy)](M = Zn(1), Cu(2)). They have been successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction reveals that two complexes are isostructural and crystallize in orthorhombic system with space group Pbcn. All L^(2-) ligands bridge metal ions to form an infinite 1D Z-shaped chain along the a axis. Then through 4,4'-bipy, contiguous Z-shaped chains are linked to form a 2D layer structure. The luminescent studies of the H2L ligand and complex 1 in the solid state and thermogravimetric analyses(TGA) of two complexes are investigated.
基金Supported by the National Natural Science Foundation of China(No.21373178)the Natural Scientific Research Foundation of Shaanxi Provincial Education Office of China(No.13JS124)
文摘Two new coordination polymers {[Zn2L1（2,2＇-bpy）2（H2O）2]·4H2O}n（1） and [Zn2L2（2,2＇-bpy）2（H2O）2]n（2）（H4L1 = terphenyl-2,2＇,4,4＇-tetracarboxylic acid, H4L2 = quarterphenyl-2,2＇,4,4＇-tetracarboxylic acid, and 2,2＇-bpy = 2,2＇-bipyridine） have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction studies. Complex 1 displays 2D wavelike networks, which are further joined together through O–H···O hydrogen bonds to give a 3D supramolecular network. Complex 2 exhibits 1D ladder-like chains, and they are further joined together by π-π stacking and O–H···O hydrogen bonding interactions to form a 3D supramolecular network. The results indicate that the backbone of carboxylate ligands has significant effects on the formation and structure of the resulting functional coordination polymers. Additionally, thermal stability and photoluminescent properties of 1 and 2 are also investigated in detail.
基金Supported by the National Natural Science Foundation of China(21101156 and 61376002)State Key Laboratory of Structure Chemistry(No.20150016)+1 种基金Outstanding Youth of Colleges and Universities of Department of Education,Fujian Province Natural Science Foundation for Youths(No.2016J05109)Fujian Education Department(No.JK2015056)
文摘The single crystals and powder of a Yavapaiite Structure phosphate,namely,PbSb0.5Fe0.5（PO4）2,were synthesized by solid state method and characterized by X-ray single-crystal diffraction and powder diffraction.The title compound crystallizes in the monoclinic system,space group C2/c（No.15） with a = 16.716（4）,b = 5.186（7）,c = 8.130（2）A,β = 114.93（6）°,Z = 4,R（I 〉 2s（I）） = 0.0430,R indices（all data） = 0.0460,and T = 293（2） K.The title compound belongs to the Yavapaiite Structure A^（Ⅱ）M^（Ⅳ）（PO4）2 compounds,and the Sb1 atom and Fe1 atoms occupy the same site（M） and their occupancy factors are refined to be 0.5 and 0.5 having a sum occupancy factor of 1.0.Its structure consists of [M（PO）4]n^2n- layers running parallel to the（b,c） plane built up of cornerconnected MO6 octahedra and PO4 tetrahedra.Additionally,the calculations of energy band structure,and density of states have been performed with the density functional theory method.The studies of computational calculation and UV experimental results show that the new compound is an indirect band-gap insulator.
文摘A new complex [Co（4,4＇-bpy）2（H2O）2（4-FBA）2]·（4,4＇-bpy）（1） has been hydro-thermally synthesized using cobalt,4,4＇-bipyridyl（4,4＇-bpy） and 4-fluorobenzoic acid（4-HFBA）,and characterized by thermal analysis,single-crystal X-ray diffraction and magnetic property.The complex crystallizes in the triclinic system,space group P,Z = 1.Crystal data：C54H44CoF2N8O6,Mr = 997.90,a = 9.134（2）,b = 11.555（2）,c = 12.867（3） ,α = 66.02（3）,β = 77.96（3）,= 73.11（3）°,V = 1180.9（4） 3,Dc = 1.403 g/cm3,μ（MoKα） = 0.433 mm-1,F（000） = 517,the final R = 0.0633 and wR = 0.1171 for 2152 observed reflections（I 〉 2σ（I））.The title complex is assembled into 1D supramolecular chains parallel to [001] based on the adjacent molecular ··· stacking interactions and hydrogen bonds.The variable temperature magnetic measurements show a weak ferromagnetic behavior over 300-160 K followed by antiferromagnetic behavior below 160 K for the title complex.
基金Financial supports received from the scientific research foundation of Sanming University(No.B201406/Q)Education Scientific Research Project of Fujian Province(No.JA15480)
文摘A new uranium（Ⅵ）-polycarboxylate framework with honeycomb（6,3） nets {[Zn（phen）_2（H_2O）_2][（UO_2）_2（BDC）_3]·2H_2O}n（1, BDC = benzene-1,4-dicarboxylate） was hydrotherrmally synthesized by the reactions of Zn（NO_3）_2·6H_2O with phenanthroine, UO_2（NO_3）_2·6H_2O and benzene-1,4-dicarboxylate. The complex was structurally characterized by FT-IR spectroscopy, powder XRD and X-ray single-crystal diffraction. Crystal data for 1： monoclinic, space group Cc with M_r = 1522.19, a = 14.9385（10）, b = 20.4922（13）, c = 15.9728（10） ？, β = 100.1240（10）°, V = 4813.5（5） ？~3, Z = 4, D_c = 2.100 g？cm^（–3）, μ = 7.293 mm^（–1）, F（000） = 2872, the final R = 0.0224 and w R= 0.0677 for 6522 observed reflections with I 〉 2σ（I）. Hydrogen bonds and π-π stacking interactions contribute to the structural extension and stabilization. Experimental band gap of about 3.57 e V indicates its broad gap semiconductor nature. UV-Vis spectra and solid-state luminescence were discussed in detail. The compound exhibits photocatalytic activities for the degradation of rhodamine B.
基金funded by the National Natural Science Foundation of China(51575004)the General Program of Beijing Municipal Education Commission(KM201610009005)
文摘β-LiZnPO4 single crystal was successfully synthesized via hydrothermal method.It crystallizes in the trigonal space group R3 with a = b = 13.6490 A, c = 9.1123 A, γ = 120.00° andZ = 18. Structure of the crystal is constructed by LiO4, ZnO4 and PO4 tetrahedral units to form athree-dimensional （3D） framework. The crystal has a high transmission ranging from 350 to 800nm with UV cut-offedge at 220 nm. The nonlinear optical efficiency of the as-prepared β-LiZnPO4is about 1.2 times as large as that of KDP （KH2PO4） standard. Additionally, band structure anddensity of states calculations for β-LiZnPO4 were performed using the total-energy code CASTEEbased on density functional theory （DFT）.
基金the National Basic Research Program of China (No. 2004CB720605)the National Natural Science Foundation of China (20373073 and 90201015)+1 种基金the Science Foundation of Fujian Province (No. E0210028)the Foundation of State Key Laboratory of Structural Chemistry (No. 060007)
文摘The single crystal and crystallized powder of triphosphate CeP3O9 have been synthesized, and the space group of CeP3O9has been determined to be C2221 with the cell parameters ofa = 8.6059, b = 11.2437, c = 7.3518 A, V= 711.4（3） A^3, Z= 4, D,. = 3.520 g/cm^3, F（000） = 700, R = 0.0377 and wR = 0.0930. The absorption and emission spectra have been measured, for which the strongest absorption and emission peaks are located at 280 and 320 nm, respectively. The density of state （DOS） and dielectric function have been calculated by the DFT method. The crystal is transparent provided the wavelength is larger than 341 nm, and the observed ultraviolet cut-off edge is at about 350 nm for a polycrystalline power sample. It is possible that the triphosphate CeP3O9 will become an ultraviolet emission material.
基金Project supported by the Natural Science Foundation of Fujian Province (E0310016) and the Education Committee Foundation of Fujian Province (JB05309)
文摘A new molybdenum phosphate [Zn（Mo^v6P4O31H10）2（C4H144N3）2].2C4H13N3.8H2O 1 （C4H13N3 = diethylenetriamine） has been synthesized under hydrothermal condition. Single-crystal X-ray diffraction reveals that compound 1 crystallizes in the monoclinic, space group P21/n, a = 13.1679（3）, b = 22.1240（6）, c = 13.6146（3） A, β= 103.4847（7）°, V = 3856.95（16） A^3, C16H90N12O70P8ZnMo12, Mr = 3035.41, Z = 2, Dc = 2.614 g/cm^3, μ = 2.483 mm^-1, F（000） = 2968, S = 1.014, the final R = 0.0196 and wR = 0.0506 for 7486 observed reflections （1 〉 2σ（I））. Compound 1 consists of two identical rings of six edge-sharing MoOt, octahedra interconnected by one ZnO6 octahedron, whereas the PO4 tetrahedra which share their apices with the MoO6, octahedra are only located on one side of each Mo6, ring. The 2-charge of polyanion [Zn（Mo^v6P4O31H10）2]^2- unit is compensated in the crystal by two mono-protonated diethylenetriamines （C4H14N3）^＋. By hydrogen bonding interactions the polyanion of compound 1 is interconnected to form pseudo threedimensional molybdophosphate. Other characterizations by elemental analyses, IR spectrum and fluorescent spectrum are also described.
基金supported by the National Natural Science Foundation of China under Projects 91422303,21571020,and 21671023
文摘In recent years, motivated by the discovery of deep-UV（wavelengths below 200 nm） nonlinear optical（NLO） phosphates, Ba3P3O（10）X（Cl, Br）, phosphates have entered into a passionate research era. In this review, recently discovered phosphate materials containing different anionic groups, i.e., isolated [PO4], [P2O7] dimer, [P3O（10）] trimer, and [PO3]∞ chain, are summarized, including their syntheses, structures, NLO performances and properties. Especially phosphates with short absorption edges in the deep-UV region and good SHG efficiency are introduced in detail. We hope that this work will present a clear view of the crystal chemistry of phosphates and promote the discovery of new high-performing second-order NLO materials to meet the urgent needs in laser science.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 29831010) and the Foundation of the State Key Laboratory of Coordination Chemistry of Nanjing University.
文摘Two ternary complexes Cu2A4[OP(OCH3)3]2 (A represents CH2=CH-COO- and CH2=C(CH3)-COO-) have been synthesized, and elemental analyses, IR, ESR, electronic reflectance spectra and magnetic studies were carried out. The single crystal X-ray diffraction shows that Cu2[CH2=C(CH3)-COO]4[OP(OCH3)3]2 is triclinic, with space group P1, a = 1.05128(13), b = 1.7559(5), c = 1.94479(3) nm, α =91.263(14)°,(β = 102.559(6)°,γ= 106.339(13)°, Z = 4 and R = 0.0668. Two copper(Ⅱ) atoms are bridged by four (a-methacrylate groups, and each copper(Ⅱ) atom is coordinated with a trimethyl phosphate molecule in the axial position, forming a distorted square pyramidal configuration. The symmetric center is between the two copper(Ⅱ) atoms, and the Cu-Cu bond distance is 0.26098(6) nm. The Cu-Cu distance and magnetic studies suggest that there exist anti-ferromagnetic interactions between the two copper(Ⅱ) atoms.
