The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-（＋）-leucinol with Ni（II） chloride and L-（-）-leucinol with Co（II） acetate tetra- hydrate in anhydrous met...The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-（＋）-leucinol with Ni（II） chloride and L-（-）-leucinol with Co（II） acetate tetra- hydrate in anhydrous methanol. The crystal structures of I and II were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Ni（C18H45N3O3）]Cl2, orthorhombic, P212121, a = 11.2807（9）, b = 14.7115（11）, c = 16.3580（13） A, V = 2714.7（4） A3, Z = 4, Pcalcd = 1.177 Mg/m3, the final R = 0.0407, and 16539 reflections observed with I 〉 2σ（/）; For II： [Co（C45HI08N6015）], trigonal, R3：H, a = 23.981（3）, b =23.981（3）, c = 10.8925（15） A, γ = 120°, V = 5425.1（14） A3, Z = 3, Pcalcd = 1.002 Mg/m3, the final R = 0.0625 for 16556 observed reflections with I 〉 2σ（I）. The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by IH NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.展开更多
Two three-dimensional supramolecular water architectures,[Zn(phen)3]2 ·[Zn(C10H16O4)·(H2O)3]·(C10H16O4)2·20H2O(1) and [Co(phen)3]2 ·[Co(H2O)6]·(C10H16O4)3·30H2O(2)[phen=1,10-Phenanth...Two three-dimensional supramolecular water architectures,[Zn(phen)3]2 ·[Zn(C10H16O4)·(H2O)3]·(C10H16O4)2·20H2O(1) and [Co(phen)3]2 ·[Co(H2O)6]·(C10H16O4)3·30H2O(2)[phen=1,10-Phenanthroline,C10H16O4=sebacic dianion],have been synthesized and characterized by IR,elemental analysis,thermogravimetric analysis,and single-crystal X-ray diffractions.The two structures both contain extensive hydrogen bonding between water molecules as well as between water molecules and sebacic anions.The water molecules and sebacic acid O atoms assembled 2D supramolecular corrugated sheets with different morphology in the two complexes.展开更多
The cobalt（II） complex with （quinolin-8-yloxy）acetate, [CoCl（C11H8NO3）]n （1）, has been prepared via the solvothermal method and characterized by IR, elemental analysis, UV- Vis diffuse-reflection spectra and s...The cobalt（II） complex with （quinolin-8-yloxy）acetate, [CoCl（C11H8NO3）]n （1）, has been prepared via the solvothermal method and characterized by IR, elemental analysis, UV- Vis diffuse-reflection spectra and single-crystal X-ray diffraction analysis. Complex 1 is a novel carboxylate-bridged one-dimensional helical cobalt（II） polymer, and the Co（II） centre exhibits an approximately square pyramidal CoClNO3 coordination geometry. It crystallizes in monoclinic, space group P21/n, with a = 9.1594（10）, b = 6.8864（7）, c = 17.290（2） , β = 102.629（3）o, C11H8ClCoNO3, Mr = 296.56, V = 1064.2（2） 3, Z = 4, Dc = 1.851 g/cm3, F（000） = 596, μ = 1.856 mm-1, the final R = 0.0308 and wR = 0.0807. Interestingly, the chain complexes are assembled to form two-dimensional networks through intermolecular face-to-face π-π stacking interactions with the centroid-to-centroid distance of 3.559（1） and the dihedral angle of 8.4（1）° between the aromatic rings.展开更多
A new complex [Co（NIT-1′-MeBzIm）2Cl2]（NIT-1′-MeBzIm = 2-{2′-[（l′-methyl）-benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by X-ray diffraction ...A new complex [Co（NIT-1′-MeBzIm）2Cl2]（NIT-1′-MeBzIm = 2-{2′-[（l′-methyl）-benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by X-ray diffraction method.The complex crystallizes in the monoclinic system,space group C2/c,Z = 4.Crystal data：C30H38Cl2CoN8O4,Mr = 704.51,a = 17.074（3）,b = 21.350（3）,c = 11.6962（19）,β = 108.879（2）°,V = 4034.3（11）3,Dc = 1.160 g/cm3,μ（MoKα） = 0.597 mm-1,F（000） = 1468,R = 0.0422 and wR = 0.1141 for 2577 observed reflections with I 2σ（I）.X-ray analysis reveals that the Co（Ⅱ） ion is six-coordinated with a distorted octahedral geometry.Temperature dependence of susceptibility measurements shows the existence of antiferromagnetic interactions between the Co（Ⅱ） ion and the radicals（J =-52.88 cm-1）.展开更多
A new Co（ll） coordination polymer has been successfully synthesized under hydrothermal conditions [Co（C2O4）（mbix）]n （1, H2C2O4 = oxalic acid, mbix = 1,3-bis（imidazol- l-ylmethyl）benzene）. Its structure has b...A new Co（ll） coordination polymer has been successfully synthesized under hydrothermal conditions [Co（C2O4）（mbix）]n （1, H2C2O4 = oxalic acid, mbix = 1,3-bis（imidazol- l-ylmethyl）benzene）. Its structure has been determined by elemental analyses, IR, UV spectroscopy and single-crystal X-ray diffraction analysis. Pink crystals crystallize in the triclinic system, space group PI with a = 8.8666（7）, b = 9.5859（8）, c = 10,8537（9） A,α = 67.6810（10）,β= 66.1260（10）, γ = 77.1300（10）°, V= 777.77（11）, CI6HI4CoN404, Mr = 385.24, Dc = 1.645 g/cm3, F（000） = 394, Z= 2,/z（MoKa） = 1.134 mm% the final R = 0.0482 and wR = 0.1231 for 2968 observed reflections （I〉 2σ（I））. It shows a two-dimensional （2D） network structure. The intermolecular C-H…O hydrogen bonding and π-π stacking interactions extend complex 1 into a 3D supramolecular architecture and play an important role in stabilizing 1. In addition, Natural Bond Orbital （NBO） analysis was performed by using the PBE0/LANL2DZ method built in Gaussian 09 Program. The calculation results showed obvious covalent interaction between the coordinated atoms and Co（II） ion.展开更多
A noval cobalt(II) coordination polymer, {[Co(bpmb)(H2O)2(C2H5OH)2]?NO3)2}∞ (1), where bpmb=N,N'- bis(3-pyridylmethyl)-1,4-benzenedicarboxamide, was synthesized by self-assembly of the two topic ligands with coba...A noval cobalt(II) coordination polymer, {[Co(bpmb)(H2O)2(C2H5OH)2]?NO3)2}∞ (1), where bpmb=N,N'- bis(3-pyridylmethyl)-1,4-benzenedicarboxamide, was synthesized by self-assembly of the two topic ligands with cobalt nitrate in ethanol solution, and characterized structurally by X-ray crystallography analysis. The crystal data belong to triclinic, space group P1with cell parameters a=0.8911(3) nm, b=0.9042(3) nm, c=1.0068(3) nm, =73.083(5)? =81.069(5)? =76.210(5)? R1=0.0518, wR2=0.0947. The results of structure analysis indicate that each bpmb ligand coordinates two Co(II) atoms and each metal atom is in octahedral coordination geometry with four oxygen atoms of two ethanol and two water molecules, two nitrogen atoms from two different bpmb ligands in trans position forming an infinite 1D chain-like structure. There are hydrogen bonding and - stacking interaction among these chains,leading to supramolecular formation with 3D net structure.展开更多
A novel compound [Co(IM2-Py)2(NO3)]?(NO3) (IM2-Py = 2-(2?-pyridyl)-4,4,5,5- tetramethylimidazoline-1-oxyl) has been prepared and structurally characterized by X-ray diffrac- tion method. It crystallizes in orthorhom...A novel compound [Co(IM2-Py)2(NO3)]?(NO3) (IM2-Py = 2-(2?-pyridyl)-4,4,5,5- tetramethylimidazoline-1-oxyl) has been prepared and structurally characterized by X-ray diffrac- tion method. It crystallizes in orthorhombic, space group P212121 with a = 11.031(2), b = 13.492(3), c = 20.467(4) ?, V = 3046.0(11) ?3, C24H32CoN8O8, Mr = 619.51, Z = 4, Dc = 1.351 g/cm3, μ(MoKα) = 0.620 mm?1, F(000) = 1292, R = 0.0506 and wR = 0.0845 for 3752 observed reflections with I > 2σ(I). X-ray analysis reveals that the crystal structure consists of [Co(IM2- Py)2(NO3)]+ moiety and a NO3 anion. The cobalt(II) ion is six-coordinated with a distorted octahedral geometry. Tempera- ? ture dependence of susceptibility measurements show that there exist an antiferromagnetic inter- action in the compound.展开更多
The title compound [Co(IM2-Py)(PCA)(N3)2] (IM2-Py = 2-(2?-pyridyl)-4,4,5,5-te- tramethylimidazoline-1-oxyl, PCA = 2-pyridine carboxylic acid) has been prepared and structurally characterized by elemental analysis, I...The title compound [Co(IM2-Py)(PCA)(N3)2] (IM2-Py = 2-(2?-pyridyl)-4,4,5,5-te- tramethylimidazoline-1-oxyl, PCA = 2-pyridine carboxylic acid) has been prepared and structurally characterized by elemental analysis, IR spectra and X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 13.169(3), b = 11.235(2), c = 15.596(3) ?, β = 104.70(3)o, V = 2232.0(8) ?3, C18H21CoN10O3, Mr = 484.38, Z = 4, Dc = 1.441 g/cm3, μ(MoKα) = 0.811 mm-1, F(000) = 1000, the final R = 0.0563 and wR = 0.1010. The nitronyl nitroxide (NIT2Py) was reduced to IM2-Py, and another NIT2Py oxidated to PCA. The self-redox reaction between the radicals was observed. The cobalt(II) ion is six-coordinated into a distorted octahedral geometry. Meanwhile, the intermolecular hydrogen bonds result in the dimer.展开更多
The authors have prepared supramolecular systems as artificial metalloproteins composed of several chiral salen-type Mn（II） and Co（II） complexes in a HSA （human serum albumin） matrix. The docking was discussed b...The authors have prepared supramolecular systems as artificial metalloproteins composed of several chiral salen-type Mn（II） and Co（II） complexes in a HSA （human serum albumin） matrix. The docking was discussed by UV-vis spectral changes and a ligand-protein docking simulation program. After linearly polarized UV light irradiation, that anisotropy of molecular orientation of the complexes increased was confirmed by polarized IR spectra. The authors have observed that the electrochemical behavior of the aligned complexes incorporating diphenyl groups in HSA can be tuned without UV radiation damage of HSA higher structures.展开更多
The Co（II） complex I and ammonium salt II were synthesized from the direct reaction of 1,2-ethylenediamine and cobaltous acetate tetrahydrate and manganese acetate tetrahydrate in anhydrous ethanol. Treatment of N,N...The Co（II） complex I and ammonium salt II were synthesized from the direct reaction of 1,2-ethylenediamine and cobaltous acetate tetrahydrate and manganese acetate tetrahydrate in anhydrous ethanol. Treatment of N,N＇-bis（salicylidene）ethylenediamine with Cu（OAc）2·H2O results in the formation of Cu（II） complex III. C14H37CoNaO8 （I）： triclinic, space group P1, a = 8.6296（12）, b = 12.0291（17）, c = 12.1108（17） A, α = 75.335（2）, β = 69.991（2）, γ = 72.248（2）°, V= 1109.4（3） A3, Z = 2, ρcaloa = 1.342 g/cm3, the final R= 0.0342 for 4817 observed reflections with I 〉 2σ（I） and Rw = 0.1263 for all data. C6H16N204 （II）： space group P1, a = 5.5513（10）, b = 5.5589（11）, c = 7.4437（14） A, α = 94.332（4）, β = 104.497（4）, γ = 103.487（4）°,V= 214.06（7） A3, Z = 1, ρcalcd = 1.398 g/cm3, the final R = 0.0431 for 829 observed reflections with I〉 2σ（I） and Rw = 0.1263 for all data. C14H37CuN40 （III）, space group P21/n, a = 9.050（9）, b = 18.434（17）, c = 11.659（11） A, β = 107.134（19）°, V= 1859（3） A3, Z = 4, ρcalcd =1.443 g/cm3, the final R = 0.0616 for 3308 observed reflections （O 〉 2σ（I）） and Rw = 0.1229 for all data. Their structures were all determined by X-ray diffraction, elemental analysis and IR.展开更多
文摘The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-（＋）-leucinol with Ni（II） chloride and L-（-）-leucinol with Co（II） acetate tetra- hydrate in anhydrous methanol. The crystal structures of I and II were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Ni（C18H45N3O3）]Cl2, orthorhombic, P212121, a = 11.2807（9）, b = 14.7115（11）, c = 16.3580（13） A, V = 2714.7（4） A3, Z = 4, Pcalcd = 1.177 Mg/m3, the final R = 0.0407, and 16539 reflections observed with I 〉 2σ（/）; For II： [Co（C45HI08N6015）], trigonal, R3：H, a = 23.981（3）, b =23.981（3）, c = 10.8925（15） A, γ = 120°, V = 5425.1（14） A3, Z = 3, Pcalcd = 1.002 Mg/m3, the final R = 0.0625 for 16556 observed reflections with I 〉 2σ（I）. The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by IH NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.
文摘Two three-dimensional supramolecular water architectures,[Zn(phen)3]2 ·[Zn(C10H16O4)·(H2O)3]·(C10H16O4)2·20H2O(1) and [Co(phen)3]2 ·[Co(H2O)6]·(C10H16O4)3·30H2O(2)[phen=1,10-Phenanthroline,C10H16O4=sebacic dianion],have been synthesized and characterized by IR,elemental analysis,thermogravimetric analysis,and single-crystal X-ray diffractions.The two structures both contain extensive hydrogen bonding between water molecules as well as between water molecules and sebacic anions.The water molecules and sebacic acid O atoms assembled 2D supramolecular corrugated sheets with different morphology in the two complexes.
基金Supported by the Science and Technology Foundation of Ministry of Development of China (2010-K6-8)Science Foundation of Suzhou University of Science and Technology
文摘The cobalt（II） complex with （quinolin-8-yloxy）acetate, [CoCl（C11H8NO3）]n （1）, has been prepared via the solvothermal method and characterized by IR, elemental analysis, UV- Vis diffuse-reflection spectra and single-crystal X-ray diffraction analysis. Complex 1 is a novel carboxylate-bridged one-dimensional helical cobalt（II） polymer, and the Co（II） centre exhibits an approximately square pyramidal CoClNO3 coordination geometry. It crystallizes in monoclinic, space group P21/n, with a = 9.1594（10）, b = 6.8864（7）, c = 17.290（2） , β = 102.629（3）o, C11H8ClCoNO3, Mr = 296.56, V = 1064.2（2） 3, Z = 4, Dc = 1.851 g/cm3, F（000） = 596, μ = 1.856 mm-1, the final R = 0.0308 and wR = 0.0807. Interestingly, the chain complexes are assembled to form two-dimensional networks through intermolecular face-to-face π-π stacking interactions with the centroid-to-centroid distance of 3.559（1） and the dihedral angle of 8.4（1）° between the aromatic rings.
基金supported by the National Natural Science Foundation of China (Nos.20771054 and 21071074)the Henan Tackle Key Problem of Science and Technology(No.0524220001)
文摘A new complex [Co（NIT-1′-MeBzIm）2Cl2]（NIT-1′-MeBzIm = 2-{2′-[（l′-methyl）-benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been prepared and structurally characterized by X-ray diffraction method.The complex crystallizes in the monoclinic system,space group C2/c,Z = 4.Crystal data：C30H38Cl2CoN8O4,Mr = 704.51,a = 17.074（3）,b = 21.350（3）,c = 11.6962（19）,β = 108.879（2）°,V = 4034.3（11）3,Dc = 1.160 g/cm3,μ（MoKα） = 0.597 mm-1,F（000） = 1468,R = 0.0422 and wR = 0.1141 for 2577 observed reflections with I 2σ（I）.X-ray analysis reveals that the Co（Ⅱ） ion is six-coordinated with a distorted octahedral geometry.Temperature dependence of susceptibility measurements shows the existence of antiferromagnetic interactions between the Co（Ⅱ） ion and the radicals（J =-52.88 cm-1）.
基金supported by the Science and Technology Development Project of Jilin Provincial Science&Technology Department(201205080)the Science and Technology Research Projects of the Education Office of Jilin Province(No.2013.384)
文摘A new Co（ll） coordination polymer has been successfully synthesized under hydrothermal conditions [Co（C2O4）（mbix）]n （1, H2C2O4 = oxalic acid, mbix = 1,3-bis（imidazol- l-ylmethyl）benzene）. Its structure has been determined by elemental analyses, IR, UV spectroscopy and single-crystal X-ray diffraction analysis. Pink crystals crystallize in the triclinic system, space group PI with a = 8.8666（7）, b = 9.5859（8）, c = 10,8537（9） A,α = 67.6810（10）,β= 66.1260（10）, γ = 77.1300（10）°, V= 777.77（11）, CI6HI4CoN404, Mr = 385.24, Dc = 1.645 g/cm3, F（000） = 394, Z= 2,/z（MoKa） = 1.134 mm% the final R = 0.0482 and wR = 0.1231 for 2968 observed reflections （I〉 2σ（I））. It shows a two-dimensional （2D） network structure. The intermolecular C-H…O hydrogen bonding and π-π stacking interactions extend complex 1 into a 3D supramolecular architecture and play an important role in stabilizing 1. In addition, Natural Bond Orbital （NBO） analysis was performed by using the PBE0/LANL2DZ method built in Gaussian 09 Program. The calculation results showed obvious covalent interaction between the coordinated atoms and Co（II） ion.
文摘A noval cobalt(II) coordination polymer, {[Co(bpmb)(H2O)2(C2H5OH)2]?NO3)2}∞ (1), where bpmb=N,N'- bis(3-pyridylmethyl)-1,4-benzenedicarboxamide, was synthesized by self-assembly of the two topic ligands with cobalt nitrate in ethanol solution, and characterized structurally by X-ray crystallography analysis. The crystal data belong to triclinic, space group P1with cell parameters a=0.8911(3) nm, b=0.9042(3) nm, c=1.0068(3) nm, =73.083(5)? =81.069(5)? =76.210(5)? R1=0.0518, wR2=0.0947. The results of structure analysis indicate that each bpmb ligand coordinates two Co(II) atoms and each metal atom is in octahedral coordination geometry with four oxygen atoms of two ethanol and two water molecules, two nitrogen atoms from two different bpmb ligands in trans position forming an infinite 1D chain-like structure. There are hydrogen bonding and - stacking interaction among these chains,leading to supramolecular formation with 3D net structure.
基金This work was supported by the National Natural Science Foundation of China (No. 20471026) and Natural Science Foundation of Henan Province (No. 0311021200)
文摘A novel compound [Co(IM2-Py)2(NO3)]?(NO3) (IM2-Py = 2-(2?-pyridyl)-4,4,5,5- tetramethylimidazoline-1-oxyl) has been prepared and structurally characterized by X-ray diffrac- tion method. It crystallizes in orthorhombic, space group P212121 with a = 11.031(2), b = 13.492(3), c = 20.467(4) ?, V = 3046.0(11) ?3, C24H32CoN8O8, Mr = 619.51, Z = 4, Dc = 1.351 g/cm3, μ(MoKα) = 0.620 mm?1, F(000) = 1292, R = 0.0506 and wR = 0.0845 for 3752 observed reflections with I > 2σ(I). X-ray analysis reveals that the crystal structure consists of [Co(IM2- Py)2(NO3)]+ moiety and a NO3 anion. The cobalt(II) ion is six-coordinated with a distorted octahedral geometry. Tempera- ? ture dependence of susceptibility measurements show that there exist an antiferromagnetic inter- action in the compound.
基金This work was supported by the Natural Science Foundation of Henan Province (No. 0311021200)
文摘The title compound [Co(IM2-Py)(PCA)(N3)2] (IM2-Py = 2-(2?-pyridyl)-4,4,5,5-te- tramethylimidazoline-1-oxyl, PCA = 2-pyridine carboxylic acid) has been prepared and structurally characterized by elemental analysis, IR spectra and X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 13.169(3), b = 11.235(2), c = 15.596(3) ?, β = 104.70(3)o, V = 2232.0(8) ?3, C18H21CoN10O3, Mr = 484.38, Z = 4, Dc = 1.441 g/cm3, μ(MoKα) = 0.811 mm-1, F(000) = 1000, the final R = 0.0563 and wR = 0.1010. The nitronyl nitroxide (NIT2Py) was reduced to IM2-Py, and another NIT2Py oxidated to PCA. The self-redox reaction between the radicals was observed. The cobalt(II) ion is six-coordinated into a distorted octahedral geometry. Meanwhile, the intermolecular hydrogen bonds result in the dimer.
文摘The authors have prepared supramolecular systems as artificial metalloproteins composed of several chiral salen-type Mn（II） and Co（II） complexes in a HSA （human serum albumin） matrix. The docking was discussed by UV-vis spectral changes and a ligand-protein docking simulation program. After linearly polarized UV light irradiation, that anisotropy of molecular orientation of the complexes increased was confirmed by polarized IR spectra. The authors have observed that the electrochemical behavior of the aligned complexes incorporating diphenyl groups in HSA can be tuned without UV radiation damage of HSA higher structures.
文摘The Co（II） complex I and ammonium salt II were synthesized from the direct reaction of 1,2-ethylenediamine and cobaltous acetate tetrahydrate and manganese acetate tetrahydrate in anhydrous ethanol. Treatment of N,N＇-bis（salicylidene）ethylenediamine with Cu（OAc）2·H2O results in the formation of Cu（II） complex III. C14H37CoNaO8 （I）： triclinic, space group P1, a = 8.6296（12）, b = 12.0291（17）, c = 12.1108（17） A, α = 75.335（2）, β = 69.991（2）, γ = 72.248（2）°, V= 1109.4（3） A3, Z = 2, ρcaloa = 1.342 g/cm3, the final R= 0.0342 for 4817 observed reflections with I 〉 2σ（I） and Rw = 0.1263 for all data. C6H16N204 （II）： space group P1, a = 5.5513（10）, b = 5.5589（11）, c = 7.4437（14） A, α = 94.332（4）, β = 104.497（4）, γ = 103.487（4）°,V= 214.06（7） A3, Z = 1, ρcalcd = 1.398 g/cm3, the final R = 0.0431 for 829 observed reflections with I〉 2σ（I） and Rw = 0.1263 for all data. C14H37CuN40 （III）, space group P21/n, a = 9.050（9）, b = 18.434（17）, c = 11.659（11） A, β = 107.134（19）°, V= 1859（3） A3, Z = 4, ρcalcd =1.443 g/cm3, the final R = 0.0616 for 3308 observed reflections （O 〉 2σ（I）） and Rw = 0.1229 for all data. Their structures were all determined by X-ray diffraction, elemental analysis and IR.
