The title compound, [Cu2（C7H5O2）4（C2H6O）2], was synthesized by the reaction of benzoic acid, copper acetate and ethanol in an aqueous solution. Trypan blue dye exclusion method was used in experiment. X-ray single...The title compound, [Cu2（C7H5O2）4（C2H6O）2], was synthesized by the reaction of benzoic acid, copper acetate and ethanol in an aqueous solution. Trypan blue dye exclusion method was used in experiment. X-ray single-crystal analysis has revealed that compound 1 （C32H32Cu2O10） crystallizes in the monoclinic system, space group C2/c, Mr = 703.66, a = 47.340（5）, b = 6.6613（4）, c = 22.028（2）A,β = 113.284（4）°, V = 6380.6（10） A^3, Z = 8, Dc= 1.465 g/cm^3, F（000） = 2896,μ = 1.388 mm^-11, the final R = 0.0515 and wR = 0.1172 for 5712 observed reflections with I 〉 2σ（I）. X-ray crystal structure analysis suggests that compound [CH2（C7H5O2）4（C2H6O）2] has a binuclear structure with two Cu（II） atoms coordinated by four benzoate groups and two ethanol molecules. The crystal packing is stabilized by intermolecular O-H...O hydrogen bonds. The compound inhibits the proliferation of K562 cells （chronic myeloid leukemic cells） significantly and dose-dependently in 48 h, and IC50 of K562 is 17.3μg/mL by trypan blue dye exclusion method.展开更多
Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen ...Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction(HER).In this study,the intrinsically tunable internal bond electric field(IBEF)at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field(IMEF)induced by the donor-acceptor(D-A)structure for an efficient HER.The aligned orientation of IBEF and IMEF resulted in a remarkable H_(2) evolution rate of 57.3 mmol·g^(-1)·h^(-1)on TNCA,which was approximately 520 times higher than that of TCNA(0.11 mmol·g^(-1)·h^(-1))with the opposing electric field orientation.The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer,kinetically facilitat-ing the migration of photogenerated electrons from D to A.Furthermore,theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only pro-vides a strong driving force for carrier transfer but also effectively hinders the return of free elec-trons to the valence band,improving the utilization of photoelectrons.This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.展开更多
Two isostructural layered coordination polymers constructed from mixed ligands, [Ln2（tdc）3（phen）2（H2O）2] （Ln = Sm 1, Eu 2, H2tdc = thiophene-2,5-dicarboxylic acid, phen = 1,10-phenanthroline）, have been hydrot...Two isostructural layered coordination polymers constructed from mixed ligands, [Ln2（tdc）3（phen）2（H2O）2] （Ln = Sm 1, Eu 2, H2tdc = thiophene-2,5-dicarboxylic acid, phen = 1,10-phenanthroline）, have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Crystal data for 1： triclinic, space group P1 with a = 10.546（2）, b = 11.201（2）, c = 18.644（4）A, α = 106.69（3）, β = 91.27（3）, γ = 94.43（3）°, Dc = 1.909 g·cm-3, F（000） = 1180, μ = 2.992 mm^-1, Z = 2, the final R = 0.0300 and wR = 0.0656 for 6968 observed reflections with I 〉 2σ（I）. And those for 2： triclinic, space group P1^- with a = 10.557（2）, b = 11.159（2）, c = 18.588（2） A, α = 106.945（6）, β = 91.255（6）, γ = 94.359（6）°, Dc = 1.927 g·cm^-3, F（000） = 1184, μ = 3.204 mm^-1, Z = 2, the final R = 0.0221 and wR = 0.0459 for 6328 observed reflections with I 〉 2σ（I）. The title complexes show a two-dimensional （2D） square grid structure constructed from paddle-wheel-like [Ln2（CO2）4] dimers and tdc ligands. The 2D layers were further assembled into a 3D supramolecular assembly via O-H…O hydrogen bond. The photoluminescence properties of complexes 1 and 2 were investigated.展开更多
Two cadmium arsonate coordination polymers, Cd（HL1）2 （1, H2L1 = 4-aminophenylarsonatic acid） and Cd（H2L2）2·2H2O （2, H3L2 = 2-（4-arsonphenylamino）acetic acid）, have been synthesized and characterized by ...Two cadmium arsonate coordination polymers, Cd（HL1）2 （1, H2L1 = 4-aminophenylarsonatic acid） and Cd（H2L2）2·2H2O （2, H3L2 = 2-（4-arsonphenylamino）acetic acid）, have been synthesized and characterized by IR and single-crystal X-ray diffraction. Crystal data for 1： triclinic, space group P1 with a = 5.7559（12）, b = 7.0903（14）, c = 8.9925（18）, α = 89.04（3）, β = 80.79（3）, γ = 85.09（3）o, Dc = 2.496 g·cm-3, μ = 6.095 mm-1, F（000） = 260, Z = 1, the final R = 0.0574 and wR = 0.1376 for 1489 observed reflections with I 〉 2σ（I）. And those for 2： monoclinic, space group P21/c with a = 4.7595（10）, b = 9.925（2）, c = 22.609（5）, β = 91.81（3）°, Dc = 2.167 g·cm-3, μ = 4.168 mm-1, F（000） = 684, Z = 2, the final R = 0.0335 and wR = 0.0815 for 2340 observed reflections with I 〉 2σ（I）. The structure of 1 shows a two-dimensional layer consisting of inorganic chains of {CdN2（AsO3）2} along the a axis linking with the phenyl groups. These layers are further linked through strong interlayer hydrogen bonding interaction to form a three-dimensional hydrogen bond supramolecular architecture. Compound 2 has inorganic chains of {CdO2（AsO3）2} similar to 1, which connect with four adjacent inorganic chains forming a three-dimensional framework.展开更多
Two zinc arsonate coordination polymers, Zn（4-apa）·H2O （1, 4-apaH2 = 4-amino- phenylarsonatic acid） and Zn（4-apa） （2）, have been hydrothermally synthesized and characterized by elemental analysis, IR and ...Two zinc arsonate coordination polymers, Zn（4-apa）·H2O （1, 4-apaH2 = 4-amino- phenylarsonatic acid） and Zn（4-apa） （2）, have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal and powder X-ray diffraction. Crystal data for 1： monoclinic, space group C2/c with a = 23.056（5）, b = 5.4224（11）, c = 15.027（3） , β = 121.22（3）°, V = 1606.6（6） ？3, Dc = 2.468 g·cm-3, F（000） = 1168, μ = 7.122 mm-1, Z = 8, the final R = 0.0309 and wR = 0.0752 for 1763 observed reflections with I 〉 2σ（I）. For 2： monoclinic, space group P21/c with a = 8.7852（18）, b = 9.2744（19）, c = 9.752（2） , β = 103.45（3）°, V = 772.7（3）3, Dc = 2.410 g·cm-3, F（000） = 544, μ = 7.387 mm-1, Z = 4, the final R = 0.0321 and wR = 0.0741 for 1696 observed reflections with I 〉 2σ（I）. The structure of 1 shows a two-dimensional （4,4）-network composed of an inorganic ladder chain bridged by the phenyl-linkers of 4-apa ligands. Compound 2 exhibits a 3D layer-pillared framework with crb net, in which inorganic （4-82）-networks are joined by the phenyl-linkers.展开更多
The reaction of Ni（CH3COO）2-4H2O, Na2MoO4·H2O, MoO3, 1,10-phenanthroline and 1,4-butylenediphosphonic acid in distilled water at 180℃ for 72 h produced two new compounds： {[Ni（1,10-phen）3][Ni（1,10-phen）2...The reaction of Ni（CH3COO）2-4H2O, Na2MoO4·H2O, MoO3, 1,10-phenanthroline and 1,4-butylenediphosphonic acid in distilled water at 180℃ for 72 h produced two new compounds： {[Ni（1,10-phen）3][Ni（1,10-phen）2（Mo6O18）（O3P（CH2）4PO3）]·6H2O}n 1 in 15% yield and {[Ni（1,10-phen）2（H2O）2] [Ni（1,10-phen）2 （H2O）（Mo5O15）（O3P（CH2）4PO3）]·6H2O} n 2 in 47% yield. 1 and 2 both feature {MonO3nO3P（CH2）4PO3}^4-（n=5, 6） 1-D anionic chain, which is further decorated and charge compensated by [Ni（1,10-phen）2]^2＋. 1 contains {Mo6O24P2} cluster constructed of three pairs of face-sharing {MoO6} octahedra linked through corner-sharing interaction. 2 exhibits the characteristic structure based on pentanuclear ring of comer- and edge-sharing {MoO6} octahedra capped by three oxygen atoms of {PO3} on each side. The thermogravimetric analyses and magnetic property of 2 were also studied.展开更多
Treatment of bis(diphenylphosphino)methane(dppm)and 2-(diphenylphosphanyl)pyridine(dpppy)with Cu(CH_(3)CN)_(4)BF_(4)afforded a dinuclear Cu(I)complex[Cu_(2)(dpppy)_(2)(dppm)(CH_(3)CN)](BF_(4))_(2)·3CH_(2)Cl_(2)(1...Treatment of bis(diphenylphosphino)methane(dppm)and 2-(diphenylphosphanyl)pyridine(dpppy)with Cu(CH_(3)CN)_(4)BF_(4)afforded a dinuclear Cu(I)complex[Cu_(2)(dpppy)_(2)(dppm)(CH_(3)CN)](BF_(4))_(2)·3CH_(2)Cl_(2)(1).Complex 1 was structurally characterized by X-ray single-crystal analysis and its photophysical properties were studied in detail.It crystallizes in triclinic space group P1^(-)with a=13.0834(8),b=13.5568(8),c=21.8544(11)Å,α=76.090(5)°,β=80.803(5)°,γ=64.582(6)°,V=3391.3(3)Å^(3),Z=2,M_(r)=1507.42,D_(c)=1.476 g/cm^(3),F(000)=1532,GOOF=1.071,the final R=0.0700 for 9041 observed reflections with I>2σ(I)and wR=0.2063 for all data.The complex contains a Cu_(2)-core structure surrounded by one dppm and two dpppy ligands in a head-to-head arrangement.In the crystalline phase,complex 1 exhibits bright bluish-green photoluminescence(λ_(max)=488 nm)with high quantum yield(ϕ=0.57)at room temperature.It is still a relatively high emission quantum yield(ϕ=0.36)in doped PMMA thin film with 20 wt%dopant of complex 1.The emission peaks of 1 in dichloromethane solution and doped PMMA(20 wt%)thin films are 510 and 494 nm,respectively,showing a very slight bathochromic shift compared to that in crystalline phase.This phenomenon might be attributed to its rigid conformation that precludes the possible distortion of copper centers in the excited state.展开更多
基金supported by the Natural Science Foundation of Fujian Province (No Z0516028) DAIICHI PHARMACEUTICAL (BEIJING) CO, LTD (No 06B004)
文摘The title compound, [Cu2（C7H5O2）4（C2H6O）2], was synthesized by the reaction of benzoic acid, copper acetate and ethanol in an aqueous solution. Trypan blue dye exclusion method was used in experiment. X-ray single-crystal analysis has revealed that compound 1 （C32H32Cu2O10） crystallizes in the monoclinic system, space group C2/c, Mr = 703.66, a = 47.340（5）, b = 6.6613（4）, c = 22.028（2）A,β = 113.284（4）°, V = 6380.6（10） A^3, Z = 8, Dc= 1.465 g/cm^3, F（000） = 2896,μ = 1.388 mm^-11, the final R = 0.0515 and wR = 0.1172 for 5712 observed reflections with I 〉 2σ（I）. X-ray crystal structure analysis suggests that compound [CH2（C7H5O2）4（C2H6O）2] has a binuclear structure with two Cu（II） atoms coordinated by four benzoate groups and two ethanol molecules. The crystal packing is stabilized by intermolecular O-H...O hydrogen bonds. The compound inhibits the proliferation of K562 cells （chronic myeloid leukemic cells） significantly and dose-dependently in 48 h, and IC50 of K562 is 17.3μg/mL by trypan blue dye exclusion method.
文摘Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction(HER).In this study,the intrinsically tunable internal bond electric field(IBEF)at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field(IMEF)induced by the donor-acceptor(D-A)structure for an efficient HER.The aligned orientation of IBEF and IMEF resulted in a remarkable H_(2) evolution rate of 57.3 mmol·g^(-1)·h^(-1)on TNCA,which was approximately 520 times higher than that of TCNA(0.11 mmol·g^(-1)·h^(-1))with the opposing electric field orientation.The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer,kinetically facilitat-ing the migration of photogenerated electrons from D to A.Furthermore,theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only pro-vides a strong driving force for carrier transfer but also effectively hinders the return of free elec-trons to the valence band,improving the utilization of photoelectrons.This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.
基金Supported by the Innovation Fund for Young Scientist of Fujian Province (2008F3059)Fuzhou University (XRC0645, 2007-XQ-09)
文摘Two isostructural layered coordination polymers constructed from mixed ligands, [Ln2（tdc）3（phen）2（H2O）2] （Ln = Sm 1, Eu 2, H2tdc = thiophene-2,5-dicarboxylic acid, phen = 1,10-phenanthroline）, have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Crystal data for 1： triclinic, space group P1 with a = 10.546（2）, b = 11.201（2）, c = 18.644（4）A, α = 106.69（3）, β = 91.27（3）, γ = 94.43（3）°, Dc = 1.909 g·cm-3, F（000） = 1180, μ = 2.992 mm^-1, Z = 2, the final R = 0.0300 and wR = 0.0656 for 6968 observed reflections with I 〉 2σ（I）. And those for 2： triclinic, space group P1^- with a = 10.557（2）, b = 11.159（2）, c = 18.588（2） A, α = 106.945（6）, β = 91.255（6）, γ = 94.359（6）°, Dc = 1.927 g·cm^-3, F（000） = 1184, μ = 3.204 mm^-1, Z = 2, the final R = 0.0221 and wR = 0.0459 for 6328 observed reflections with I 〉 2σ（I）. The title complexes show a two-dimensional （2D） square grid structure constructed from paddle-wheel-like [Ln2（CO2）4] dimers and tdc ligands. The 2D layers were further assembled into a 3D supramolecular assembly via O-H…O hydrogen bond. The photoluminescence properties of complexes 1 and 2 were investigated.
基金supported by the Innovation Fund for Young Scientists of Fujian Province (2008F3059)Fund of Fujian Provincial Key Laboratory of Nanomaterials (NM10-02)
文摘Two cadmium arsonate coordination polymers, Cd（HL1）2 （1, H2L1 = 4-aminophenylarsonatic acid） and Cd（H2L2）2·2H2O （2, H3L2 = 2-（4-arsonphenylamino）acetic acid）, have been synthesized and characterized by IR and single-crystal X-ray diffraction. Crystal data for 1： triclinic, space group P1 with a = 5.7559（12）, b = 7.0903（14）, c = 8.9925（18）, α = 89.04（3）, β = 80.79（3）, γ = 85.09（3）o, Dc = 2.496 g·cm-3, μ = 6.095 mm-1, F（000） = 260, Z = 1, the final R = 0.0574 and wR = 0.1376 for 1489 observed reflections with I 〉 2σ（I）. And those for 2： monoclinic, space group P21/c with a = 4.7595（10）, b = 9.925（2）, c = 22.609（5）, β = 91.81（3）°, Dc = 2.167 g·cm-3, μ = 4.168 mm-1, F（000） = 684, Z = 2, the final R = 0.0335 and wR = 0.0815 for 2340 observed reflections with I 〉 2σ（I）. The structure of 1 shows a two-dimensional layer consisting of inorganic chains of {CdN2（AsO3）2} along the a axis linking with the phenyl groups. These layers are further linked through strong interlayer hydrogen bonding interaction to form a three-dimensional hydrogen bond supramolecular architecture. Compound 2 has inorganic chains of {CdO2（AsO3）2} similar to 1, which connect with four adjacent inorganic chains forming a three-dimensional framework.
基金Financial supports received from the Fujian Provincial Key Laboratory of Nanomaterials (NM10-02)the Innovation Fund for Young Scientist of Fujian Province (2010J05022)National Natural Science Foundation of China (21001026)
文摘Two zinc arsonate coordination polymers, Zn（4-apa）·H2O （1, 4-apaH2 = 4-amino- phenylarsonatic acid） and Zn（4-apa） （2）, have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal and powder X-ray diffraction. Crystal data for 1： monoclinic, space group C2/c with a = 23.056（5）, b = 5.4224（11）, c = 15.027（3） , β = 121.22（3）°, V = 1606.6（6） ？3, Dc = 2.468 g·cm-3, F（000） = 1168, μ = 7.122 mm-1, Z = 8, the final R = 0.0309 and wR = 0.0752 for 1763 observed reflections with I 〉 2σ（I）. For 2： monoclinic, space group P21/c with a = 8.7852（18）, b = 9.2744（19）, c = 9.752（2） , β = 103.45（3）°, V = 772.7（3）3, Dc = 2.410 g·cm-3, F（000） = 544, μ = 7.387 mm-1, Z = 4, the final R = 0.0321 and wR = 0.0741 for 1696 observed reflections with I 〉 2σ（I）. The structure of 1 shows a two-dimensional （4,4）-network composed of an inorganic ladder chain bridged by the phenyl-linkers of 4-apa ligands. Compound 2 exhibits a 3D layer-pillared framework with crb net, in which inorganic （4-82）-networks are joined by the phenyl-linkers.
基金Supported by the State Key Laboratory of Structural Chemistry, the National Science and Technology of China (001CB1089), the Chinese Academy of Sciences (CAS), the National Natural Science Foundation of China (20273073, 20333070 and 90206040), Key Item of Science and Technology of Fujian Province (2004 1+201-2), the Science Foundation of CAS and Fujian Province (2002F014, 2003J042, 2004J041 and Z0513022)
文摘The reaction of Ni（CH3COO）2-4H2O, Na2MoO4·H2O, MoO3, 1,10-phenanthroline and 1,4-butylenediphosphonic acid in distilled water at 180℃ for 72 h produced two new compounds： {[Ni（1,10-phen）3][Ni（1,10-phen）2（Mo6O18）（O3P（CH2）4PO3）]·6H2O}n 1 in 15% yield and {[Ni（1,10-phen）2（H2O）2] [Ni（1,10-phen）2 （H2O）（Mo5O15）（O3P（CH2）4PO3）]·6H2O} n 2 in 47% yield. 1 and 2 both feature {MonO3nO3P（CH2）4PO3}^4-（n=5, 6） 1-D anionic chain, which is further decorated and charge compensated by [Ni（1,10-phen）2]^2＋. 1 contains {Mo6O24P2} cluster constructed of three pairs of face-sharing {MoO6} octahedra linked through corner-sharing interaction. 2 exhibits the characteristic structure based on pentanuclear ring of comer- and edge-sharing {MoO6} octahedra capped by three oxygen atoms of {PO3} on each side. The thermogravimetric analyses and magnetic property of 2 were also studied.
基金supported by the Natural Science Foundation of Fujian Province(2017J01576)。
文摘Treatment of bis(diphenylphosphino)methane(dppm)and 2-(diphenylphosphanyl)pyridine(dpppy)with Cu(CH_(3)CN)_(4)BF_(4)afforded a dinuclear Cu(I)complex[Cu_(2)(dpppy)_(2)(dppm)(CH_(3)CN)](BF_(4))_(2)·3CH_(2)Cl_(2)(1).Complex 1 was structurally characterized by X-ray single-crystal analysis and its photophysical properties were studied in detail.It crystallizes in triclinic space group P1^(-)with a=13.0834(8),b=13.5568(8),c=21.8544(11)Å,α=76.090(5)°,β=80.803(5)°,γ=64.582(6)°,V=3391.3(3)Å^(3),Z=2,M_(r)=1507.42,D_(c)=1.476 g/cm^(3),F(000)=1532,GOOF=1.071,the final R=0.0700 for 9041 observed reflections with I>2σ(I)and wR=0.2063 for all data.The complex contains a Cu_(2)-core structure surrounded by one dppm and two dpppy ligands in a head-to-head arrangement.In the crystalline phase,complex 1 exhibits bright bluish-green photoluminescence(λ_(max)=488 nm)with high quantum yield(ϕ=0.57)at room temperature.It is still a relatively high emission quantum yield(ϕ=0.36)in doped PMMA thin film with 20 wt%dopant of complex 1.The emission peaks of 1 in dichloromethane solution and doped PMMA(20 wt%)thin films are 510 and 494 nm,respectively,showing a very slight bathochromic shift compared to that in crystalline phase.This phenomenon might be attributed to its rigid conformation that precludes the possible distortion of copper centers in the excited state.
