The title coordination polymer 1,{[Cu8(btb)2(CN)8].3H2O}n(btb = 1,4-bis(1,2,4-triazol-1-yl)butane),has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 cryst...The title coordination polymer 1,{[Cu8(btb)2(CN)8].3H2O}n(btb = 1,4-bis(1,2,4-triazol-1-yl)butane),has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938(3),b = 1.9422(5),c = 0.9406(2) nm,β = 121.891(4)°,V = 2.0066(9) nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ(MoKα) = 4.209 mm?1,F(000) = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I > 2σ(I).In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.展开更多
The title complex 1,{[CuEu(Hbidc)2(H2O)4]·H2O}n(H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 cr...The title complex 1,{[CuEu(Hbidc)2(H2O)4]·H2O}n(H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1,with a = 7.791(2),b = 12.058(3),c = 12.109(3),α = 82.189(5),β = 72.407(5),γ = 89.184(4)°,V = 1073.7(5)3,C18H18CuEuN4O13,Mr = 713.86,Dc = 2.208 g/cm3,μ(MoKα) = 3.967 mm-1,F(000) = 700,GOOF = 0.950,Z = 2,the final R = 0.0531 and wR = 0.1068 for I > 2σ(I).Complex 1 possess a tape-like chain structure consisting of Eu2C8O4 and Cu2Eu2C18N4O4 metallic rings alternatively arranged and is the first 3d-4f heterometallic complex based on the 1H-ben-zimidazole-5,6-dicarboxylato ligand(Hbidc).Plenty of hydrogen-bonding and π...π stacking interactions connect the 1D chains to construct a 3D supramolecular architecture.展开更多
The title complex 1,[Cd 4 Cu 2 (pdc) 4 (H 2 O) 14 ] (H 3 pdc=3,5-pyrazoledicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes...The title complex 1,[Cd 4 Cu 2 (pdc) 4 (H 2 O) 14 ] (H 3 pdc=3,5-pyrazoledicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235(10),b=1.27935(18),c=1.28569(17) nm,α=112.633(2),β=102.971(3),γ=97.089(2)o,V=0.9673(2) nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ(MoKα)=3.356 mm 1,F(000)=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I > 2σ(Ⅰ).In 1,two deprotonated 3,5-pyrazoledicarboxylic acids (pdc 3),one copper(Ⅱ) ion and one cadmium(Ⅱ) ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium(Ⅱ) ions through chelating carboxylate groups to construct the copper(Ⅱ)-cadmium(Ⅱ) heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional (3D) supramolecular framework.展开更多
Utilizing the periodically structured metal–organic framework(MOF) as the reaction vessel is a promising technique to achieve the aligned polymer molecular chains, where the diffusion procedure of the polymer monomer...Utilizing the periodically structured metal–organic framework(MOF) as the reaction vessel is a promising technique to achieve the aligned polymer molecular chains, where the diffusion procedure of the polymer monomer inside MOF is one of the key mechanisms. To investigate the diffusion mechanism of fluorinated polymer monomers in MOFs, in this paper the molecular dynamics simulations combined with the density functional theory and the Monte Carlo method are used and the all-atom models of TFMA(trifluoroethyl methacrylate) monomer and two types of MOFs, [Zn_2(BDC)_2(TED)]n and[Zn_2(BPDC)_2(TED)]n, are established. The diffusion behaviors of TFMA monomer in these two MOFs are simulated and the main influencing factors are analyzed. The obtained results are as follows. First, the electrostatic interactions between TFMA monomers and MOFs cause the monomers to concentrate in the MOF channel, which slows down the monomer diffusion. Second, the anisotropic shape of the one-dimensional MOF channel leads to different diffusion speeds of monomers in different directions. Third, MOF with a larger pore diameter due to a longer organic ligand, [Zn_2(BPDC)_2(TED)]n in this paper, facilitates the diffusion of monomers in the MOF channel. Finally, as the number of monomers increases, the self-diffusion coefficient is reduced by the steric effect.展开更多
Complex [Mn(tce) 0.5(H2O) 4](1) was obtained from Mn(OAc) 2 and tce,where tce is 1,1,2,2-tetracarboxyl-ethane. The structure of 1 is a single molecule,in which Mn(II) is a distorted octahedron coordinated to six oxyge...Complex [Mn(tce) 0.5(H2O) 4](1) was obtained from Mn(OAc) 2 and tce,where tce is 1,1,2,2-tetracarboxyl-ethane. The structure of 1 is a single molecule,in which Mn(II) is a distorted octahedron coordinated to six oxygen atoms. Complex [Cd(tce) 0.5(H2O) 3](H2O) (2) fea-tures a pillared layer architecture. The Cd(II) atom is in an octahedral environment coordinated by six oxygen donors from water molecules and tce ligands. Cd(II) atoms are interlinked by the tce ligand to generate a 2-D wavelike layer. The layers are strutted by the intermolecular O-H···O hydrogen bonds to form a 3-D open framework. Luminescence property of complex 2 was investigated. Magnetic property of complex 1 was also studied. 1 belongs to triclinic,space group P1 with a = 6.2901(12) ,b = 8.0212(15) ,c = 8.0769(15) ,α = 108.522(3) ,β = 95.068(3) ,γ = 97.086(3) °,V = 379.92(12) 3,Mr = 456.08,Dc = 1.993 g/cm3,F(000) = 232,μ = 1.748 mm-1,Z = 1,the final R = 0.0297 and wR = 0.0731 for 1575 observed reflections with I > 2σ(I) . 2 is of monoclinic system,space group P21/c with a = 6.4367(14) ,b = 9.495(2) ,c = 13.907(3) ,β = 117.405(8) °,V = 754.6(3) 3,Mr = 285.51,Dc = 2.513 g/cm3,F(000) = 556,μ = 2.905 mm-1,Z = 4,the final R = 0.0375 and wR = 0.0737 for 1521 observed reflections with I > 2σ(I).展开更多
A new Mn(Ⅱ) coordination polymer {[Mn(timb)2(H2O)2]·(Cl)2·(H2O)2}n(1,timb = 1,3,5-tris-(imidazol-1-ylmethyl)benzene) has been synthesized and characterized by elemental analysis,IR,TG and single-crystal X-r...A new Mn(Ⅱ) coordination polymer {[Mn(timb)2(H2O)2]·(Cl)2·(H2O)2}n(1,timb = 1,3,5-tris-(imidazol-1-ylmethyl)benzene) has been synthesized and characterized by elemental analysis,IR,TG and single-crystal X-ray diffraction.The title compound crystallizes in the triclinic system,space group P1 with a=9.0774(13),b=9.8720(15),c=11.4898(16),α=93.378(3),β= 95.471(3),γ=101.101(3)°,V=1002.6(3)3,Mr=834.67,Dc=1.382 g/cm3,μ(MoKα)=0.517mm-1,F(000)=435,GOF=0.986,Z=1,the final R=0.0506 and wR=0.1139 for 3517 observed reflections I>2σ(I).It consists of one-dimensional double stranded chains formed through bridging bidentate timb ligands,and these chains are further connected to yield a 3D supramolecular framework by hydrogen bonding interactions and π…π stacking interactions.展开更多
A new terbium(III) metal-organic framework [Tb(HL)(H2O)](Tb L) based on a new synthetic ligand 9-(2,6-dicarboxy-pyridin-4-yl)-9 H-carbazole-3,6-dicarboxylic acid(H4 L) has been synthesized under solvothermal condition...A new terbium(III) metal-organic framework [Tb(HL)(H2O)](Tb L) based on a new synthetic ligand 9-(2,6-dicarboxy-pyridin-4-yl)-9 H-carbazole-3,6-dicarboxylic acid(H4 L) has been synthesized under solvothermal conditions. Its structure was determined by single-crystal X-ray diffraction analysis, and further characterized by powder X-ray diffraction analysis and IR spectra. The title complex crystallizes in trigonal space group P3212 with a = b = 13.6491(11), c = 32.345(3) ?, γ = 120°, V = 5218.5(10) ?~3, C(42)H(20)N4O(17)Tb2, Mr = 1170.46, Dc = 1.117 g/cm^3, μ(Mo Kα) = 2.065 mm^(-1), F(000) = 1698, GOF = 1.054, Z = 3, the final R = 0.0384 and wR = 0.0771 for 5223 observed reflections(I > 2s(I)). In Tb L, the tri-bridged binuclear Tb2 units are bibridged by two carbazole-3,6-dicarboxylate moieties to lead to the homochiral parallel arranged helical chains, which are further connected by 2,6-pyridinedicarboxylate moieties to produce the chiral neutral 3 D framework. There are there kinds of 1 D channels in the framework with the channel space occupying 53.3% of the total volume. TbL exhibits intense characteristic green emission of Tb^(3+) ions.展开更多
By solvothermal reaction of Cd(II)with organic ligand N,N’-bis(3,5-dicarboxylphenyl)-thiophene-2,5-dicarboxamide(H_(4)L),a water-stable complex[Cd_(4)(H_(2)L)_(4)(H_(2)O)_(10)]·2CH_(3)OH·8H_(2)O·4DMF(1...By solvothermal reaction of Cd(II)with organic ligand N,N’-bis(3,5-dicarboxylphenyl)-thiophene-2,5-dicarboxamide(H_(4)L),a water-stable complex[Cd_(4)(H_(2)L)_(4)(H_(2)O)_(10)]·2CH_(3)OH·8H_(2)O·4DMF(1,C_(102)H_(120)Cd_(4)N_(12)O_(64)S_(4))has been successfully synthetized(DMF=N,N-dimethylformamide).1 crystallizes in the triclinic space group of P1 with a=11.815(7),b=16.209(9),c=16.742(9)Å,α=82.224(13)°,β=76.741(13)°,γ=70.313(12)°,V=2932(3)Å^(3),M_(r)=3115.93,Z=1,F(000)=1584,D_(c)=1.765 Mg/cm^(3),μ=0.901 mm^(-1),GOOF=1.101,the final R=0.0391 and wR=0.1297 for 9007 observed reflections(I>2σ(I)).1 is a tetranuclear Cd(II)bicyclic complex with strong ligand-based blue emission and can stably exist in aqueous solutions over the pH range of 2~11.1exhibits high sensitivity,selectivity and anti-interference capability for picric acid(PA)detection in aqueous solution by luminescent quenching.The value of quenching constant(K_(sv))is 3.2×10^(4)M^(-1) within the PAconcentration range of 0~40μM and the detection limit is 6.89×10^(-7) M.Lastly,we went into depth on possible mechanism of the luminescent quenching.展开更多
基金Supported by Nanjing University of Posts and Telecommunications (No. NY209032)the National Natural Science Foundation of China (No. 21001065)the Major State Basic Research Development Program of China (973 Program,No. 2009CB930600)
文摘The title coordination polymer 1,{[Cu8(btb)2(CN)8].3H2O}n(btb = 1,4-bis(1,2,4-triazol-1-yl)butane),has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938(3),b = 1.9422(5),c = 0.9406(2) nm,β = 121.891(4)°,V = 2.0066(9) nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ(MoKα) = 4.209 mm?1,F(000) = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I > 2σ(I).In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.
基金Supported by the Nanjing University of Posts and Telecommunications(No.NY209032)the National Natural Science Foundation of China(No.21001065)the Major State Basic Research Development Program of China (973 Program,No.2009CB930600)
文摘The title complex 1,{[CuEu(Hbidc)2(H2O)4]·H2O}n(H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1,with a = 7.791(2),b = 12.058(3),c = 12.109(3),α = 82.189(5),β = 72.407(5),γ = 89.184(4)°,V = 1073.7(5)3,C18H18CuEuN4O13,Mr = 713.86,Dc = 2.208 g/cm3,μ(MoKα) = 3.967 mm-1,F(000) = 700,GOOF = 0.950,Z = 2,the final R = 0.0531 and wR = 0.1068 for I > 2σ(I).Complex 1 possess a tape-like chain structure consisting of Eu2C8O4 and Cu2Eu2C18N4O4 metallic rings alternatively arranged and is the first 3d-4f heterometallic complex based on the 1H-ben-zimidazole-5,6-dicarboxylato ligand(Hbidc).Plenty of hydrogen-bonding and π...π stacking interactions connect the 1D chains to construct a 3D supramolecular architecture.
基金Nanjing University of Posts and Telecommunications (No. NY209032)Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University),Ministry of Education,Science Foundation for Youths of Guangxi Province (No. 0991089)the Major State Basic Research Development Program of China (973 Program,No. 2009CB930600)
文摘The title complex 1,[Cd 4 Cu 2 (pdc) 4 (H 2 O) 14 ] (H 3 pdc=3,5-pyrazoledicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1 with a=0.67235(10),b=1.27935(18),c=1.28569(17) nm,α=112.633(2),β=102.971(3),γ=97.089(2)o,V=0.9673(2) nm 3,C 20 H 32 Cd 4 Cu 2 N 8 O 30,M r=1441.22,D c=2.474 g/cm 3,μ(MoKα)=3.356 mm 1,F(000)=698,S=1.003,Z=1,the final R=0.0471 and wR=0.0748 for I > 2σ(Ⅰ).In 1,two deprotonated 3,5-pyrazoledicarboxylic acids (pdc 3),one copper(Ⅱ) ion and one cadmium(Ⅱ) ion firstly form a pyrazole-bridged Cu II Cd II dinuclear unit,two of which related by an inversion center are connected by another two cadmium(Ⅱ) ions through chelating carboxylate groups to construct the copper(Ⅱ)-cadmium(Ⅱ) heterometallic hexanuclear complexes.Plenty of hydrogen bond interactions existing in the system further lead to a three-dimensional (3D) supramolecular framework.
基金Project supported by the National Natural Science Foundation of China(Grant No.61575096)
文摘Utilizing the periodically structured metal–organic framework(MOF) as the reaction vessel is a promising technique to achieve the aligned polymer molecular chains, where the diffusion procedure of the polymer monomer inside MOF is one of the key mechanisms. To investigate the diffusion mechanism of fluorinated polymer monomers in MOFs, in this paper the molecular dynamics simulations combined with the density functional theory and the Monte Carlo method are used and the all-atom models of TFMA(trifluoroethyl methacrylate) monomer and two types of MOFs, [Zn_2(BDC)_2(TED)]n and[Zn_2(BPDC)_2(TED)]n, are established. The diffusion behaviors of TFMA monomer in these two MOFs are simulated and the main influencing factors are analyzed. The obtained results are as follows. First, the electrostatic interactions between TFMA monomers and MOFs cause the monomers to concentrate in the MOF channel, which slows down the monomer diffusion. Second, the anisotropic shape of the one-dimensional MOF channel leads to different diffusion speeds of monomers in different directions. Third, MOF with a larger pore diameter due to a longer organic ligand, [Zn_2(BPDC)_2(TED)]n in this paper, facilitates the diffusion of monomers in the MOF channel. Finally, as the number of monomers increases, the self-diffusion coefficient is reduced by the steric effect.
基金Supported by the National Science Fund for Distinguished Young Scholars of China (No.20725104)the NNSFC (No.20531040)
文摘Complex [Mn(tce) 0.5(H2O) 4](1) was obtained from Mn(OAc) 2 and tce,where tce is 1,1,2,2-tetracarboxyl-ethane. The structure of 1 is a single molecule,in which Mn(II) is a distorted octahedron coordinated to six oxygen atoms. Complex [Cd(tce) 0.5(H2O) 3](H2O) (2) fea-tures a pillared layer architecture. The Cd(II) atom is in an octahedral environment coordinated by six oxygen donors from water molecules and tce ligands. Cd(II) atoms are interlinked by the tce ligand to generate a 2-D wavelike layer. The layers are strutted by the intermolecular O-H···O hydrogen bonds to form a 3-D open framework. Luminescence property of complex 2 was investigated. Magnetic property of complex 1 was also studied. 1 belongs to triclinic,space group P1 with a = 6.2901(12) ,b = 8.0212(15) ,c = 8.0769(15) ,α = 108.522(3) ,β = 95.068(3) ,γ = 97.086(3) °,V = 379.92(12) 3,Mr = 456.08,Dc = 1.993 g/cm3,F(000) = 232,μ = 1.748 mm-1,Z = 1,the final R = 0.0297 and wR = 0.0731 for 1575 observed reflections with I > 2σ(I) . 2 is of monoclinic system,space group P21/c with a = 6.4367(14) ,b = 9.495(2) ,c = 13.907(3) ,β = 117.405(8) °,V = 754.6(3) 3,Mr = 285.51,Dc = 2.513 g/cm3,F(000) = 556,μ = 2.905 mm-1,Z = 4,the final R = 0.0375 and wR = 0.0737 for 1521 observed reflections with I > 2σ(I).
基金Supported by the National Basic Research Program of China (2006CB806104)Science Foundation for Youths of Guangxi Province (No 0991089)Initiation Found of Hechi University (No 2008QS-N022)
文摘A new Mn(Ⅱ) coordination polymer {[Mn(timb)2(H2O)2]·(Cl)2·(H2O)2}n(1,timb = 1,3,5-tris-(imidazol-1-ylmethyl)benzene) has been synthesized and characterized by elemental analysis,IR,TG and single-crystal X-ray diffraction.The title compound crystallizes in the triclinic system,space group P1 with a=9.0774(13),b=9.8720(15),c=11.4898(16),α=93.378(3),β= 95.471(3),γ=101.101(3)°,V=1002.6(3)3,Mr=834.67,Dc=1.382 g/cm3,μ(MoKα)=0.517mm-1,F(000)=435,GOF=0.986,Z=1,the final R=0.0506 and wR=0.1139 for 3517 observed reflections I>2σ(I).It consists of one-dimensional double stranded chains formed through bridging bidentate timb ligands,and these chains are further connected to yield a 3D supramolecular framework by hydrogen bonding interactions and π…π stacking interactions.
基金supported by the National Natural Science Foundation of China (21271143)Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) (YX03001)+1 种基金Jiangsu Province Double Innovation Talent Program (090300014001)Nanjing University of Posts & Telecommunications (NY212004)
基金supported by the National Natural Science Foundation of China(21973047)。
文摘A new terbium(III) metal-organic framework [Tb(HL)(H2O)](Tb L) based on a new synthetic ligand 9-(2,6-dicarboxy-pyridin-4-yl)-9 H-carbazole-3,6-dicarboxylic acid(H4 L) has been synthesized under solvothermal conditions. Its structure was determined by single-crystal X-ray diffraction analysis, and further characterized by powder X-ray diffraction analysis and IR spectra. The title complex crystallizes in trigonal space group P3212 with a = b = 13.6491(11), c = 32.345(3) ?, γ = 120°, V = 5218.5(10) ?~3, C(42)H(20)N4O(17)Tb2, Mr = 1170.46, Dc = 1.117 g/cm^3, μ(Mo Kα) = 2.065 mm^(-1), F(000) = 1698, GOF = 1.054, Z = 3, the final R = 0.0384 and wR = 0.0771 for 5223 observed reflections(I > 2s(I)). In Tb L, the tri-bridged binuclear Tb2 units are bibridged by two carbazole-3,6-dicarboxylate moieties to lead to the homochiral parallel arranged helical chains, which are further connected by 2,6-pyridinedicarboxylate moieties to produce the chiral neutral 3 D framework. There are there kinds of 1 D channels in the framework with the channel space occupying 53.3% of the total volume. TbL exhibits intense characteristic green emission of Tb^(3+) ions.
基金supported by the National Natural Science Foundation of China(21973047)Jiangsu Province Double Innovation Talent Program(090300014001)。
文摘By solvothermal reaction of Cd(II)with organic ligand N,N’-bis(3,5-dicarboxylphenyl)-thiophene-2,5-dicarboxamide(H_(4)L),a water-stable complex[Cd_(4)(H_(2)L)_(4)(H_(2)O)_(10)]·2CH_(3)OH·8H_(2)O·4DMF(1,C_(102)H_(120)Cd_(4)N_(12)O_(64)S_(4))has been successfully synthetized(DMF=N,N-dimethylformamide).1 crystallizes in the triclinic space group of P1 with a=11.815(7),b=16.209(9),c=16.742(9)Å,α=82.224(13)°,β=76.741(13)°,γ=70.313(12)°,V=2932(3)Å^(3),M_(r)=3115.93,Z=1,F(000)=1584,D_(c)=1.765 Mg/cm^(3),μ=0.901 mm^(-1),GOOF=1.101,the final R=0.0391 and wR=0.1297 for 9007 observed reflections(I>2σ(I)).1 is a tetranuclear Cd(II)bicyclic complex with strong ligand-based blue emission and can stably exist in aqueous solutions over the pH range of 2~11.1exhibits high sensitivity,selectivity and anti-interference capability for picric acid(PA)detection in aqueous solution by luminescent quenching.The value of quenching constant(K_(sv))is 3.2×10^(4)M^(-1) within the PAconcentration range of 0~40μM and the detection limit is 6.89×10^(-7) M.Lastly,we went into depth on possible mechanism of the luminescent quenching.
