A novel compound 4,8,10-trimethyl-2-(3,5-dimethylpyrazol)-pyrido-[2',3':3,4]-py-razol-[1,5-5-a]-pyrimidine(C17H18N6) has been synthesized from 2,6-dichloro-4-methylnico-tino-nitrile,hydrazine and acetylacetone ...A novel compound 4,8,10-trimethyl-2-(3,5-dimethylpyrazol)-pyrido-[2',3':3,4]-py-razol-[1,5-5-a]-pyrimidine(C17H18N6) has been synthesized from 2,6-dichloro-4-methylnico-tino-nitrile,hydrazine and acetylacetone by substitution and cyclolization.The structure was charac-terized by elemental analysis,1H NMR and IR,and single-crystal structure was determined by X-ray diffraction analysis.The compound crystallizes in the monoclinic system,space group P21/c with a = 8.0338(9),b = 28.618(3),c = 7.2688(8),β = 111.051(2)o,V = 1559.6(3) 3,Z = 4,Dc = 1.305 g/cm3,μ = 0.083 mm-1,Mr = 306.37,F(000) = 648,S = 0.971,the final R = 0.0795 and wR = 0.1746 for 1457 observed reflections(Ⅰ 〉 2σ(Ⅰ)).The results demonstrate that the pyridine,pyrazole and pyrimidine rings are nearly coplanar,which is evident from the dihedral angles among the four rings in the range of 0.13~4.15o.The face-to-face π-π stacking interactions among pyridine,pyrazol and pyrimidine rings result in a supramolecular crystal,in which they seem to be effective in stabilizing the structure.Meanwhile,the fluorescence properties of the title compound were discussed,which showed very strong fluorescence.The calculated results(selected bond lengths,bond angles and torsion angles) are all typical and agree well with the experimental results,which demonstrates that B3LYP/6-31+G* is suitable for the title compound.展开更多
A novel materials design procedure based on the co-doping of metal nanoparticle and azo dye compound (MNPADC) is developed to improve the properties of functional molecules. The synthesized materials were characteri...A novel materials design procedure based on the co-doping of metal nanoparticle and azo dye compound (MNPADC) is developed to improve the properties of functional molecules. The synthesized materials were characterized by transmission electron micrograph (TEM), ultraviolet-visible absorption spectra (UV-Vis) and fluorescence spectra (FS). It was found that the fluorescence intensity of methyl orange (MO) was enhanced by 5 times in the aqueous composite system doped with silver nanoparticles whereas it was reduced by 15% and 20% in composite films with co-mixing and coating structures, respectively. The results indicate that the properties of functional molecules can be greatly improved in composite film with supra molecular structure and that the procedure presented here is effective.展开更多
Two coordination polymers(CPs),{[Ag(ADA)(0.5)(DPE)]·H2O}n(1) and {[Ag(ADA)(0.5)(Bipy)(0.5)]·H2O}n(2),(H2ADA = 3,3-azodibenzoic acid,DPE = 1,2-di(4-pyridyl)-ethylene,Bipy = 4,4?-bipyri...Two coordination polymers(CPs),{[Ag(ADA)(0.5)(DPE)]·H2O}n(1) and {[Ag(ADA)(0.5)(Bipy)(0.5)]·H2O}n(2),(H2ADA = 3,3-azodibenzoic acid,DPE = 1,2-di(4-pyridyl)-ethylene,Bipy = 4,4?-bipyridine),have been synthesized via solvothermal reactions of Ag+ with ADA^2- and/or DPE,Bipy.CPs 1 and 2 were characterized by elemental analyses,IR spectra,thermal behaviors,and X-ray single-crystal diffraction.CPs 1 and 2 feature "Ag···Ag" subunits.CP 1 shows a 3D construction,in which the "Ag···Ag" subunits extend through ADA^2- and DPE ligands using μ6-kO,O;kO;kO;kO,O;kO;kO and μ2-kO;kO coordination modes,respectively.It crystallizes in triclinic system,space group P1,with a = 0.3808(18),b = 1.2476(6),c = 1.309(6) nm,α = 76.757(5),β = 84.649(5),γ = 86.809(5)o,V = 0.6024(5) nm^3,Z = 2,Mr = 351.11,C(13)H(11)AgN2O3,Dc = 1.936 g/cm3,F(000) = 348,S = 1.064,R = 0.0323 and w R = 0.0689.CP 2 exhibits a 3 D supramolecular structure,in which the "Ag···Ag" subunits are connected by ADA^2- and DPE ligands with μ6-kO;kO;kO,O;kO;kO and μ2-kO;kO coordination modes,respectively.Ultimately,through hydrogen bond and π···π interaction,the "Ag···Ag" subunits stabilize the 3D supramolecular structure of 2.It crystallizes in monoclinic,space group C2/c,with a = 25.301(15),b = 13.197(8),c = 6.970(4) nm,β = 102.597(7)o,V = 2.271(2) nm^3,Z = 8,C(12)H(10)AgN2O(2.50),Mr = 330.09,Dc = 1.931 g/cm^3,F(000) = 1304,S = 1.082,R = 0.1107 and wR = 0.2984.The fluorescence properties of CPs 1 and 2 have been also investigated.展开更多
Two dehydroabietic acid-based arylamines have been synthesized and characterized by FTIR, 1H NMR, 13C NMR, MS spectra and elemental analysis. Their spatial structures were determined by X-ray diffraction analysis. UV-...Two dehydroabietic acid-based arylamines have been synthesized and characterized by FTIR, 1H NMR, 13C NMR, MS spectra and elemental analysis. Their spatial structures were determined by X-ray diffraction analysis. UV-Vis absorption and fluorescence spectral characteristics of these compounds in methanol were investigated. Their fluorescence emission spectra in different polarity solvents were further evaluated. Fluorescent properties and structural relationship of the compounds showed that fluorescence intensity and quantum yield inversely increase with the non-coplanar degree. In addition, the solvent polarity has different effects on the fluorescence emission spectra of two compounds.展开更多
A new pseudo three-dimensional framework structure of the title compound {[CuⅡ(1,10-phen)]2[PMoⅥ11MoⅤO40]}[CuⅠ(C8N4H6)(C9H6NO)(H2O)](1) has been prepared by the hydrothermal method for the first time and...A new pseudo three-dimensional framework structure of the title compound {[CuⅡ(1,10-phen)]2[PMoⅥ11MoⅤO40]}[CuⅠ(C8N4H6)(C9H6NO)(H2O)](1) has been prepared by the hydrothermal method for the first time and characterized by elemental analyses,X-ray single-crystal diffraction and IR spectra.1 consists of two building blocks,one {[CuⅡ(1,10-phen)]2[PMoⅥ11MoⅤO40]} and one [CuⅠ(C8N4H6)(C9H6NO)(H2O)] coordinated group.Singlecrystal X-ray diffraction revealed that 1 crystallizes in the monoclinic system,space group P2/c with a=13.498(4),b=12.890(3),c=21.465(8),β=97.314o,V=3704(2)3,Mr=2693.61,Z=2,Dc=2.415 Mg/m3,μ=2.915 mm-1,F(000)=2562,S=1.009,the final R=0.0583 and wR=0.1406 for 5129 observed reflections with I2σ(I).Furthermore,compound 1 shows strong fluorescent properties in the solid state at room temperature.The electrochemical behavior of 1 has also been studied by cyclic voltammograms.展开更多
An organically templated 2-D uranyl sulfate, {(C2H8N)[(UO2)Cl(SO4)(H2O)] }n 1, has been hydrothermally synthesized. The crystal and molecular structures have been determined by X-ray crystallography method and...An organically templated 2-D uranyl sulfate, {(C2H8N)[(UO2)Cl(SO4)(H2O)] }n 1, has been hydrothermally synthesized. The crystal and molecular structures have been determined by X-ray crystallography method and spectral techniques. 1 belongs to monoclinic, space group P21/c with a = 8.3545(17), b = 10.550(2), c = 12.370(3)A, β = 102.64(3)°, V = 1063.9(4)A3, Mr = 464.64, De= 2.901 g/cm^3, F(000) = 836,μ = 15.710 mm^-1, Z= 4, the final R = 0.0286 and wR = 0.0685 for 10164 observed reflections with Ⅰ 〉 2σ(Ⅰ). 1 presents a two-dimensional layer-like structure constructed from infinite anionic [(UO2)Cl(H2O)(SO4)]^- layers with [C2H8N]^+ cations balancing the charge and a number of intermoleeular hydrogen bonds (C-H…O and O-H…Cl) existing in the solid state. The fluorescence properties of 1 have also been discussed.展开更多
One coordination polymer(CP) {[Mn(ADA)(Phen)](H2O)2}n(1, H2ADA = azobenzene-4,4'-dicarboxylic acid, Phen = 1,10-phenanthroline), has been synthesized via hydrothermal reactions. CP 1 was characterized by el...One coordination polymer(CP) {[Mn(ADA)(Phen)](H2O)2}n(1, H2ADA = azobenzene-4,4'-dicarboxylic acid, Phen = 1,10-phenanthroline), has been synthesized via hydrothermal reactions. CP 1 was characterized by elemental analyses, IR spectra, thermal behaviors, and X-ray single-crystal diffraction. In CP 1, each ADA(2-) ligand bridges two Mn(2+) to give one-dimensional zigzag chains with the Mn···Mn separations of 17.6911 and 16.3976 A, which generates a three-dimensional supramolecular structure by means of strong π···π interaction and hydrogen bonding. It crystallizes in triclinic, space group P1, with a = 7.6200(13), b = 9.1530(15), c = 18.262(2) A, α = 88.467(3)o, β = 84.145(2)o, γ = 77.542(2)o, V = 1237.2(3) A3, Z = 2, C(26)H(20)MnN4O6, Mr = 539.40, Dc = 1.448 g/cm3, F(000) = 554, S = 1.018, R = 0.0531 and w R = 0.1094. In addition, natural bond orbital analysis was performed by the B3 LYP/LANL2 DZ method of Gaussian 09 Program. The fluorescence, magnetic, and electrochemical properties of 1 have been investigated.展开更多
A new boron compound [C27H21BN4O3] based on 2-(2?-hydroxyphenyl)-1 Hbenzimidazole has been synthesized and characterized by single-crystal X-ray diffraction, and its crystal crystallizes in the monoclinic system, spac...A new boron compound [C27H21BN4O3] based on 2-(2?-hydroxyphenyl)-1 Hbenzimidazole has been synthesized and characterized by single-crystal X-ray diffraction, and its crystal crystallizes in the monoclinic system, space group P21/n with a = 9.6544(5), b = 14.1558(8), c = 16.4314(9) ?, β = 97.730°, Mr = 460.29, V = 2225.2(2) ?~3, Z = 4, Dc = 1.374 g/cm~3, μ = 0.74 mm-1, S = 1.051, F(000) = 960, the final R = 0.0643 and w R = 0.1569 for 2233 observed reflections(I > 2σ(I)). The title compound is a B(III) center mononuclear molecule in the asymmetric unit. The typical structural characteristic of the title compound is the methanol group adopting a μ2-bridging mode to link two different adjacent chelating modes though two types of hydrogen bonds to form a one-dimensional supramolecular structure. Additionally, aromatic π-π stacking interactions between adjacent benzimidazolyl groups lead to a three-dimensional network. Furthermore, the stability and fluorescence property revealed the potential applications in the organic photoelectric material.展开更多
A new complex [Cd(H2biim)2(H2O)2]·(ino)2·4H2O (H2biim = 2,2'-biimidazole, ino = isonicotinate-N-oxide) has been prepared and characterized by single-crystal X-ray diffraction analysis, IR and fluore...A new complex [Cd(H2biim)2(H2O)2]·(ino)2·4H2O (H2biim = 2,2'-biimidazole, ino = isonicotinate-N-oxide) has been prepared and characterized by single-crystal X-ray diffraction analysis, IR and fluorescence spectra analysis. The crystal is of triclinic system, space group P1 with a = 7.5380(6), b = 8.0402(7), c = 13.5094(11) , α = 104.269(1), β = 93.604(1), γ = 98.349(1)°, V = 780.93(11) 3, Mr = 765.00, Dc = 1.627 g/cm3, F(000) = 390, μ = 0.776 mm-1 and Z = 1. The final R = 0.0322 and wR = 0.0825 for 7038 observed reflections with I 2σ(I) and R = 0.0341 and wR = 0.0832 for all data. The title complex exhibits an infinite chain-like structure through bridging isonicotinate-N-oxide. Strong interchain hydrogen bonds between isonicotinate-N-oxide and H2biim result in the robust 3-D supramolecular architecture. Moreover, the complex shows strong photoluminescence with emission maximum at λ = 401 nm upon λex = 330 nm.展开更多
A Keggin-type tungstohosphate compound [Cu^l(2,2'-bipy)2]3[PW^Ⅵ12O40] 1 (bipy = bipyddine) was prepared by the hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 (C60H48Cu3...A Keggin-type tungstohosphate compound [Cu^l(2,2'-bipy)2]3[PW^Ⅵ12O40] 1 (bipy = bipyddine) was prepared by the hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 (C60H48Cu3N12O40PW12) crystallizes in the monoclinic system, space group P21/c with a = 16.9837(10), b = 17.9732(13) c = 27.8701(13)A°, β = 96.1039(10)°, V = 8459.2(9) A°^3, Mr = 4004.89, Z = 4, Dc = 3.145 g/cm^3, μ = 17.089 mm^-1, F(000) = 7208, S = 1.005, the final R = 0.0469 and wR = 0.0827 for 10807 observed reflections (I 〉 2σ(I)). Compound 1 consists of one discrete normal Keggin polyanion [PW^Ⅵ 12O40]^3- and three isolated coordinated cations [Cu^1(2,2'-bipy)2]^+. Significantly, there exist three crystallographically independent asymmetric reduced copper (I) centers in 1. Furthermore, the compound shows strong photoluminescence property in solid state at room temperature.展开更多
A novel silver(I) complex [Ag(2,2ˊ-bipy)(C14H9O3)]·(C14H10O3) has been synthesized with 2-benzoylbenzoic acid as the ligand. Crystal data for the title complex: monoclinic, space group Cc, a = 27.4089...A novel silver(I) complex [Ag(2,2ˊ-bipy)(C14H9O3)]·(C14H10O3) has been synthesized with 2-benzoylbenzoic acid as the ligand. Crystal data for the title complex: monoclinic, space group Cc, a = 27.4089(13), b = 10.2897(5), c = 12.0024(6)A, β = 111.864(4)°, Mr = 715.49, V = 3141.5(3) A3, Dc = 1.513 g/cm^3, Z = 4, μ(Mo Kα) = 0.694 mm^-1, F(000) = 1456, the final R = 0.0473 and w R = 0.1146. In the title complex, the central Ag(I) ion is located in a triangular coordination environment. The electron transfer is quasi-reversible in the electrode reaction and it shows a strong emission peak in the range of 495-520 nm under 502 nm excitation. In addition, it displays diamagnetic property from 3 to 300 K.展开更多
A new 3D cobalt metal-organic framework [C_7H_(13)N_2]_2[(CH_3COO)_2Co_7(oba)_5-(Hoba)_2(OH)_2]·H_2O has been synthesized under ionothermal conditions and characterized by elemental analysis, FT-IR, XRD...A new 3D cobalt metal-organic framework [C_7H_(13)N_2]_2[(CH_3COO)_2Co_7(oba)_5-(Hoba)_2(OH)_2]·H_2O has been synthesized under ionothermal conditions and characterized by elemental analysis, FT-IR, XRD, and TG. This complex crystallizes in monoclinic system, space group P21/c with a = 19.4499(4), b = 10.8839(2), c = 27.7796(5) ?, β = 104.467(2)o, V = 5694.22(19) ?~3, Z = 2, C_(116)H_(92)Co_7N_4O_(42), M_r = 2626.45, D_c = 1.532 g/cm^3 , F(000) = 2682, μ = 1.085 mm-1, R = 0.0387 and wR = 0.1177. Its structure is characterized as a 3D open framework constructed by seven nuclear clusters [(CH_3COO)_Co_7(OH)_2] and the 4,4?-oxybisbenzoic acid ligand. The used ILs cations are located in the middle of the pore and compensate for the negative charges of framework. Furthermore, its fluorescence property has also been studied.展开更多
A new infinite three-dimensional framework structure of the title compound [H6Mo^VI8O27]·3C4N2H10 has been synthesized under mild hydrothermal conditions and characterized by elemental analyses, IR, fluorescent s...A new infinite three-dimensional framework structure of the title compound [H6Mo^VI8O27]·3C4N2H10 has been synthesized under mild hydrothermal conditions and characterized by elemental analyses, IR, fluorescent spectra and single-crystal X-ray diffraction. C12H36Mo8N6O27 crystallizes in the triclinic system, space group P1^- with a = 8.820(3), b = 9.534(3), c = 10.993(4)A, α= 99.985(17), β = 106.65(2), γ= 101.650(14)°,V = 840.6(5)A^3, Mr = 1463.99, Z = 1, Dc = 2.892 g/cm^3,μ = 2.993 mm^-1, F(000) = 702, the final R = 0.0676, wR = 0.1920 and S = 1.074 for 2196 observed reflections with I 〉 2σ(I). The title compound exhibits a novel infinite three-dimensional (3D) framework composed of a [H6Mo^VI8O27] subunit and three dissociated piperazine fragments. The complex exhibits two strong fluorescent emission bands at ca. 417 and 440 nm (λex = 378nm) in the solid state at room temperature.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
A new one-dimensional(1D) polymer, [Zn(HMIDC)(bpy)]n·2n H2O(1, H3MIDC = 2-methyl-imidazole-4,5-dicarboxylic acid, bpy = 2,2-bipyridine), has been solvothermally synthesized and characterized by single-cry...A new one-dimensional(1D) polymer, [Zn(HMIDC)(bpy)]n·2n H2O(1, H3MIDC = 2-methyl-imidazole-4,5-dicarboxylic acid, bpy = 2,2-bipyridine), has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectrum and fluorescence measurements. Complex 1 crystallizes in orthorhombic system, space group Pbca with a = 14.404(3), b = 8.6900(17), c = 26.570(5) , V = 3325.8(11) -3, Dc = 1.700 g/cm-3, Mr = 425.70, Z = 8, F(000) = 1744, μ = 1.522 mm-(-1), the final R = 0.0421 and w R = 0.1018. The Zn(Ⅱ) ion is six-coordinated by O and N atoms from one HMIDC ligand, two O atoms from another HMIDC ligand and two N atoms from the bpy ligand. The HMIDC anion, which acts as a tetradentate ligand, chelates two Zn ions to form a one-dimensional(1D) zigzag chain structure. We analyzed the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with the UV-vis spectrum. And we also discussed the luminescent mechanism of complex 1 in detail.展开更多
水热法合成了一个无机-有机杂化的NH_(4)[Cu_(3)^(I)(C_(10)H_(8)N_(2))_(3)Mo_(8)O_(26)]化合物,通过元素分析和单晶X-射线衍射进行了表征。化合物为三斜晶系,P1空间群,晶胞参数a=1.08763(9)nm,b=1.12674(10)nm,c=1.13067(10)nm,α=68....水热法合成了一个无机-有机杂化的NH_(4)[Cu_(3)^(I)(C_(10)H_(8)N_(2))_(3)Mo_(8)O_(26)]化合物,通过元素分析和单晶X-射线衍射进行了表征。化合物为三斜晶系,P1空间群,晶胞参数a=1.08763(9)nm,b=1.12674(10)nm,c=1.13067(10)nm,α=68.4820(10)°,β=83.523(2)°,γ=64.4180(10)°,V=1.16095(2)nm^(3),Z=1,Dc=2.661 g/cm^(3),Mr=1860.73,μ(MoKα)=35.22 cm^(-1),F(000)=888,R=0.0478,wR=0.099。化合物的结构包含2个结晶学上独立的铜原子、不连续的多氧阴离子β-[Mo_(8)O_(2)6]4-和无限扩展的[Cu I(C_(10)H_(8)N_(2))]链。每一个铜原子为类似的{CuN_(2)}配位模式,被4,4’-联吡啶连接成一维沿a轴方向的[Cu(C 10 H 8 N 2)]+链。分子结构中存在氢键和π…π作用。对化合物的热稳定性、荧光性质也进行了研究。展开更多
基金Supported by the National Natural Science Foundation of China (20761002)the Natural Science Foundation of Guangxi Province (0832080)the Innovation Project of Guangxi Graduate Education (2008106080817M366)
文摘A novel compound 4,8,10-trimethyl-2-(3,5-dimethylpyrazol)-pyrido-[2',3':3,4]-py-razol-[1,5-5-a]-pyrimidine(C17H18N6) has been synthesized from 2,6-dichloro-4-methylnico-tino-nitrile,hydrazine and acetylacetone by substitution and cyclolization.The structure was charac-terized by elemental analysis,1H NMR and IR,and single-crystal structure was determined by X-ray diffraction analysis.The compound crystallizes in the monoclinic system,space group P21/c with a = 8.0338(9),b = 28.618(3),c = 7.2688(8),β = 111.051(2)o,V = 1559.6(3) 3,Z = 4,Dc = 1.305 g/cm3,μ = 0.083 mm-1,Mr = 306.37,F(000) = 648,S = 0.971,the final R = 0.0795 and wR = 0.1746 for 1457 observed reflections(Ⅰ 〉 2σ(Ⅰ)).The results demonstrate that the pyridine,pyrazole and pyrimidine rings are nearly coplanar,which is evident from the dihedral angles among the four rings in the range of 0.13~4.15o.The face-to-face π-π stacking interactions among pyridine,pyrazol and pyrimidine rings result in a supramolecular crystal,in which they seem to be effective in stabilizing the structure.Meanwhile,the fluorescence properties of the title compound were discussed,which showed very strong fluorescence.The calculated results(selected bond lengths,bond angles and torsion angles) are all typical and agree well with the experimental results,which demonstrates that B3LYP/6-31+G* is suitable for the title compound.
基金This work was supported by the National Natural Science Foundation of China (Grant No. 50271038)the Key Research Project Foundation of Shaanxi Normal University of China (No. 200403) Specialized Research Fund for the Doctoral Program of Higher Education of China (No. 20050698017).
文摘A novel materials design procedure based on the co-doping of metal nanoparticle and azo dye compound (MNPADC) is developed to improve the properties of functional molecules. The synthesized materials were characterized by transmission electron micrograph (TEM), ultraviolet-visible absorption spectra (UV-Vis) and fluorescence spectra (FS). It was found that the fluorescence intensity of methyl orange (MO) was enhanced by 5 times in the aqueous composite system doped with silver nanoparticles whereas it was reduced by 15% and 20% in composite films with co-mixing and coating structures, respectively. The results indicate that the properties of functional molecules can be greatly improved in composite film with supra molecular structure and that the procedure presented here is effective.
基金supported by the National Natural Science Foundation of China(21503183,21663031,21373189)the provincial level innovation programs funds of undergraduate for 2017(1573)
文摘Two coordination polymers(CPs),{[Ag(ADA)(0.5)(DPE)]·H2O}n(1) and {[Ag(ADA)(0.5)(Bipy)(0.5)]·H2O}n(2),(H2ADA = 3,3-azodibenzoic acid,DPE = 1,2-di(4-pyridyl)-ethylene,Bipy = 4,4?-bipyridine),have been synthesized via solvothermal reactions of Ag+ with ADA^2- and/or DPE,Bipy.CPs 1 and 2 were characterized by elemental analyses,IR spectra,thermal behaviors,and X-ray single-crystal diffraction.CPs 1 and 2 feature "Ag···Ag" subunits.CP 1 shows a 3D construction,in which the "Ag···Ag" subunits extend through ADA^2- and DPE ligands using μ6-kO,O;kO;kO;kO,O;kO;kO and μ2-kO;kO coordination modes,respectively.It crystallizes in triclinic system,space group P1,with a = 0.3808(18),b = 1.2476(6),c = 1.309(6) nm,α = 76.757(5),β = 84.649(5),γ = 86.809(5)o,V = 0.6024(5) nm^3,Z = 2,Mr = 351.11,C(13)H(11)AgN2O3,Dc = 1.936 g/cm3,F(000) = 348,S = 1.064,R = 0.0323 and w R = 0.0689.CP 2 exhibits a 3 D supramolecular structure,in which the "Ag···Ag" subunits are connected by ADA^2- and DPE ligands with μ6-kO;kO;kO,O;kO;kO and μ2-kO;kO coordination modes,respectively.Ultimately,through hydrogen bond and π···π interaction,the "Ag···Ag" subunits stabilize the 3D supramolecular structure of 2.It crystallizes in monoclinic,space group C2/c,with a = 25.301(15),b = 13.197(8),c = 6.970(4) nm,β = 102.597(7)o,V = 2.271(2) nm^3,Z = 8,C(12)H(10)AgN2O(2.50),Mr = 330.09,Dc = 1.931 g/cm^3,F(000) = 1304,S = 1.082,R = 0.1107 and wR = 0.2984.The fluorescence properties of CPs 1 and 2 have been also investigated.
基金supported by the National Natural Science Foundation of China (No. 31170539)
文摘Two dehydroabietic acid-based arylamines have been synthesized and characterized by FTIR, 1H NMR, 13C NMR, MS spectra and elemental analysis. Their spatial structures were determined by X-ray diffraction analysis. UV-Vis absorption and fluorescence spectral characteristics of these compounds in methanol were investigated. Their fluorescence emission spectra in different polarity solvents were further evaluated. Fluorescent properties and structural relationship of the compounds showed that fluorescence intensity and quantum yield inversely increase with the non-coplanar degree. In addition, the solvent polarity has different effects on the fluorescence emission spectra of two compounds.
基金supported by the Key Project of Chinese Ministry of Education (No 208066)Natural Science Foundation of Fujian Province (2007J0216, U0750004)+1 种基金Education Department of Fujian Province (JA07029)State Key Laboratory of Structural Chemistry (No 20080053)
文摘A new pseudo three-dimensional framework structure of the title compound {[CuⅡ(1,10-phen)]2[PMoⅥ11MoⅤO40]}[CuⅠ(C8N4H6)(C9H6NO)(H2O)](1) has been prepared by the hydrothermal method for the first time and characterized by elemental analyses,X-ray single-crystal diffraction and IR spectra.1 consists of two building blocks,one {[CuⅡ(1,10-phen)]2[PMoⅥ11MoⅤO40]} and one [CuⅠ(C8N4H6)(C9H6NO)(H2O)] coordinated group.Singlecrystal X-ray diffraction revealed that 1 crystallizes in the monoclinic system,space group P2/c with a=13.498(4),b=12.890(3),c=21.465(8),β=97.314o,V=3704(2)3,Mr=2693.61,Z=2,Dc=2.415 Mg/m3,μ=2.915 mm-1,F(000)=2562,S=1.009,the final R=0.0583 and wR=0.1406 for 5129 observed reflections with I2σ(I).Furthermore,compound 1 shows strong fluorescent properties in the solid state at room temperature.The electrochemical behavior of 1 has also been studied by cyclic voltammograms.
基金Supported by the Project of Natural Science Foundations of Fujian (No. 2008J0172)National Natural Science Foundation of China (20705031)
文摘An organically templated 2-D uranyl sulfate, {(C2H8N)[(UO2)Cl(SO4)(H2O)] }n 1, has been hydrothermally synthesized. The crystal and molecular structures have been determined by X-ray crystallography method and spectral techniques. 1 belongs to monoclinic, space group P21/c with a = 8.3545(17), b = 10.550(2), c = 12.370(3)A, β = 102.64(3)°, V = 1063.9(4)A3, Mr = 464.64, De= 2.901 g/cm^3, F(000) = 836,μ = 15.710 mm^-1, Z= 4, the final R = 0.0286 and wR = 0.0685 for 10164 observed reflections with Ⅰ 〉 2σ(Ⅰ). 1 presents a two-dimensional layer-like structure constructed from infinite anionic [(UO2)Cl(H2O)(SO4)]^- layers with [C2H8N]^+ cations balancing the charge and a number of intermoleeular hydrogen bonds (C-H…O and O-H…Cl) existing in the solid state. The fluorescence properties of 1 have also been discussed.
基金supported by the National Natural Science Foundation of China(21503183,21663031)the Provincial Level Innovation Programs Fund of undergraduate for 2017(No.D2017010)
文摘One coordination polymer(CP) {[Mn(ADA)(Phen)](H2O)2}n(1, H2ADA = azobenzene-4,4'-dicarboxylic acid, Phen = 1,10-phenanthroline), has been synthesized via hydrothermal reactions. CP 1 was characterized by elemental analyses, IR spectra, thermal behaviors, and X-ray single-crystal diffraction. In CP 1, each ADA(2-) ligand bridges two Mn(2+) to give one-dimensional zigzag chains with the Mn···Mn separations of 17.6911 and 16.3976 A, which generates a three-dimensional supramolecular structure by means of strong π···π interaction and hydrogen bonding. It crystallizes in triclinic, space group P1, with a = 7.6200(13), b = 9.1530(15), c = 18.262(2) A, α = 88.467(3)o, β = 84.145(2)o, γ = 77.542(2)o, V = 1237.2(3) A3, Z = 2, C(26)H(20)MnN4O6, Mr = 539.40, Dc = 1.448 g/cm3, F(000) = 554, S = 1.018, R = 0.0531 and w R = 0.1094. In addition, natural bond orbital analysis was performed by the B3 LYP/LANL2 DZ method of Gaussian 09 Program. The fluorescence, magnetic, and electrochemical properties of 1 have been investigated.
基金The research was supported by the Scientific and Technological Project of Henan Province(No.182102210102)the Key Scientific Research Project of Colleges and Universities of Henan Province(No.15A150061)the National Natural Science Foundation of China(Nos.21371154,61405054 and 21601156)
文摘A new boron compound [C27H21BN4O3] based on 2-(2?-hydroxyphenyl)-1 Hbenzimidazole has been synthesized and characterized by single-crystal X-ray diffraction, and its crystal crystallizes in the monoclinic system, space group P21/n with a = 9.6544(5), b = 14.1558(8), c = 16.4314(9) ?, β = 97.730°, Mr = 460.29, V = 2225.2(2) ?~3, Z = 4, Dc = 1.374 g/cm~3, μ = 0.74 mm-1, S = 1.051, F(000) = 960, the final R = 0.0643 and w R = 0.1569 for 2233 observed reflections(I > 2σ(I)). The title compound is a B(III) center mononuclear molecule in the asymmetric unit. The typical structural characteristic of the title compound is the methanol group adopting a μ2-bridging mode to link two different adjacent chelating modes though two types of hydrogen bonds to form a one-dimensional supramolecular structure. Additionally, aromatic π-π stacking interactions between adjacent benzimidazolyl groups lead to a three-dimensional network. Furthermore, the stability and fluorescence property revealed the potential applications in the organic photoelectric material.
基金supported by the National Natural Science Foundation of China (No. 20772042)
文摘A new complex [Cd(H2biim)2(H2O)2]·(ino)2·4H2O (H2biim = 2,2'-biimidazole, ino = isonicotinate-N-oxide) has been prepared and characterized by single-crystal X-ray diffraction analysis, IR and fluorescence spectra analysis. The crystal is of triclinic system, space group P1 with a = 7.5380(6), b = 8.0402(7), c = 13.5094(11) , α = 104.269(1), β = 93.604(1), γ = 98.349(1)°, V = 780.93(11) 3, Mr = 765.00, Dc = 1.627 g/cm3, F(000) = 390, μ = 0.776 mm-1 and Z = 1. The final R = 0.0322 and wR = 0.0825 for 7038 observed reflections with I 2σ(I) and R = 0.0341 and wR = 0.0832 for all data. The title complex exhibits an infinite chain-like structure through bridging isonicotinate-N-oxide. Strong interchain hydrogen bonds between isonicotinate-N-oxide and H2biim result in the robust 3-D supramolecular architecture. Moreover, the complex shows strong photoluminescence with emission maximum at λ = 401 nm upon λex = 330 nm.
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 Keggin-type tungstohosphate compound [Cu^l(2,2'-bipy)2]3[PW^Ⅵ12O40] 1 (bipy = bipyddine) was prepared by the hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 (C60H48Cu3N12O40PW12) crystallizes in the monoclinic system, space group P21/c with a = 16.9837(10), b = 17.9732(13) c = 27.8701(13)A°, β = 96.1039(10)°, V = 8459.2(9) A°^3, Mr = 4004.89, Z = 4, Dc = 3.145 g/cm^3, μ = 17.089 mm^-1, F(000) = 7208, S = 1.005, the final R = 0.0469 and wR = 0.0827 for 10807 observed reflections (I 〉 2σ(I)). Compound 1 consists of one discrete normal Keggin polyanion [PW^Ⅵ 12O40]^3- and three isolated coordinated cations [Cu^1(2,2'-bipy)2]^+. Significantly, there exist three crystallographically independent asymmetric reduced copper (I) centers in 1. Furthermore, the compound shows strong photoluminescence property in solid state at room temperature.
基金Supported by the Natural Science Foundation of Hunan Province(No.11JJ9006)Key Project of Science and Technology Plan of Hunan Province(2012FJ2002)the Construct Program of the Key Discipline in Hunan Province
文摘A novel silver(I) complex [Ag(2,2ˊ-bipy)(C14H9O3)]·(C14H10O3) has been synthesized with 2-benzoylbenzoic acid as the ligand. Crystal data for the title complex: monoclinic, space group Cc, a = 27.4089(13), b = 10.2897(5), c = 12.0024(6)A, β = 111.864(4)°, Mr = 715.49, V = 3141.5(3) A3, Dc = 1.513 g/cm^3, Z = 4, μ(Mo Kα) = 0.694 mm^-1, F(000) = 1456, the final R = 0.0473 and w R = 0.1146. In the title complex, the central Ag(I) ion is located in a triangular coordination environment. The electron transfer is quasi-reversible in the electrode reaction and it shows a strong emission peak in the range of 495-520 nm under 502 nm excitation. In addition, it displays diamagnetic property from 3 to 300 K.
基金Project supported by College Programs SNIE(No.2014ZDKJ011)
文摘A new 3D cobalt metal-organic framework [C_7H_(13)N_2]_2[(CH_3COO)_2Co_7(oba)_5-(Hoba)_2(OH)_2]·H_2O has been synthesized under ionothermal conditions and characterized by elemental analysis, FT-IR, XRD, and TG. This complex crystallizes in monoclinic system, space group P21/c with a = 19.4499(4), b = 10.8839(2), c = 27.7796(5) ?, β = 104.467(2)o, V = 5694.22(19) ?~3, Z = 2, C_(116)H_(92)Co_7N_4O_(42), M_r = 2626.45, D_c = 1.532 g/cm^3 , F(000) = 2682, μ = 1.085 mm-1, R = 0.0387 and wR = 0.1177. Its structure is characterized as a 3D open framework constructed by seven nuclear clusters [(CH_3COO)_Co_7(OH)_2] and the 4,4?-oxybisbenzoic acid ligand. The used ILs cations are located in the middle of the pore and compensate for the negative charges of framework. Furthermore, its fluorescence property has also been studied.
基金the Natural Science Foundation of Fujian Province(2007J0216,U0750004)the Ministry of Education of China(No.208066)+1 种基金the Education Department of Fujian Province(JA07029)the State Key Laboratory of Structural Chemistry(No.20080053)
文摘A new infinite three-dimensional framework structure of the title compound [H6Mo^VI8O27]·3C4N2H10 has been synthesized under mild hydrothermal conditions and characterized by elemental analyses, IR, fluorescent spectra and single-crystal X-ray diffraction. C12H36Mo8N6O27 crystallizes in the triclinic system, space group P1^- with a = 8.820(3), b = 9.534(3), c = 10.993(4)A, α= 99.985(17), β = 106.65(2), γ= 101.650(14)°,V = 840.6(5)A^3, Mr = 1463.99, Z = 1, Dc = 2.892 g/cm^3,μ = 2.993 mm^-1, F(000) = 702, the final R = 0.0676, wR = 0.1920 and S = 1.074 for 2196 observed reflections with I 〉 2σ(I). The title compound exhibits a novel infinite three-dimensional (3D) framework composed of a [H6Mo^VI8O27] subunit and three dissociated piperazine fragments. The complex exhibits two strong fluorescent emission bands at ca. 417 and 440 nm (λex = 378nm) in the solid state at room temperature.
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 Fundamental Research Foundation of Central Universities(No.142304007)Basic Key Program of Applied Basic Research of Science and Technology Commission Foundation of Hebei Province(No.15961005D)Natural Science Foundation of Liaoning Province(No.2015020665)
文摘A new one-dimensional(1D) polymer, [Zn(HMIDC)(bpy)]n·2n H2O(1, H3MIDC = 2-methyl-imidazole-4,5-dicarboxylic acid, bpy = 2,2-bipyridine), has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, UV-vis spectrum and fluorescence measurements. Complex 1 crystallizes in orthorhombic system, space group Pbca with a = 14.404(3), b = 8.6900(17), c = 26.570(5) , V = 3325.8(11) -3, Dc = 1.700 g/cm-3, Mr = 425.70, Z = 8, F(000) = 1744, μ = 1.522 mm-(-1), the final R = 0.0421 and w R = 0.1018. The Zn(Ⅱ) ion is six-coordinated by O and N atoms from one HMIDC ligand, two O atoms from another HMIDC ligand and two N atoms from the bpy ligand. The HMIDC anion, which acts as a tetradentate ligand, chelates two Zn ions to form a one-dimensional(1D) zigzag chain structure. We analyzed the electronic structure and orbital energies of complex 1 by DFT methods, and the results are consistent with the UV-vis spectrum. And we also discussed the luminescent mechanism of complex 1 in detail.
文摘水热法合成了一个无机-有机杂化的NH_(4)[Cu_(3)^(I)(C_(10)H_(8)N_(2))_(3)Mo_(8)O_(26)]化合物,通过元素分析和单晶X-射线衍射进行了表征。化合物为三斜晶系,P1空间群,晶胞参数a=1.08763(9)nm,b=1.12674(10)nm,c=1.13067(10)nm,α=68.4820(10)°,β=83.523(2)°,γ=64.4180(10)°,V=1.16095(2)nm^(3),Z=1,Dc=2.661 g/cm^(3),Mr=1860.73,μ(MoKα)=35.22 cm^(-1),F(000)=888,R=0.0478,wR=0.099。化合物的结构包含2个结晶学上独立的铜原子、不连续的多氧阴离子β-[Mo_(8)O_(2)6]4-和无限扩展的[Cu I(C_(10)H_(8)N_(2))]链。每一个铜原子为类似的{CuN_(2)}配位模式,被4,4’-联吡啶连接成一维沿a轴方向的[Cu(C 10 H 8 N 2)]+链。分子结构中存在氢键和π…π作用。对化合物的热稳定性、荧光性质也进行了研究。