Aggregation behavior of 5,10,15-tris(pentafluorophenyl)corrole (F15TPC), 5,10,15,20-tetra(pentafluoroph-enyl)porphyrin (F20TPP), and their copper complexes in DCM solution were investigated by using UV-Vis spectro-sco...Aggregation behavior of 5,10,15-tris(pentafluorophenyl)corrole (F15TPC), 5,10,15,20-tetra(pentafluoroph-enyl)porphyrin (F20TPP), and their copper complexes in DCM solution were investigated by using UV-Vis spectro-scopic method. F20TPP and F20TPPCu exhibited strong π-π stacking interactions in DCM, and the intermolecular dimerization constants turned out to be 1.82 × 103 and 17.2 × 103 L·mol-1 respectively. However, extinction coefficients of F15TPC and F15TPCCu at soret band remained unchanged with increasing in their concentrations from 1.0 to 40.0 μmol·L-1, indicating they remained monomeric in DCM solution. Based on DFT calculation and the π-π stacking geometries observed in crystal structures of metal octaethylcorrole complexes, destroy of π-π interactions in F15TPC and F15TPCCu may be understood by the electrostatic potential surfaces (EPS) features of the molecules and steric repulsions caused by the introducing of three phenyl at the meso- positions of corrole macrocycle.展开更多
利用1,10-邻菲啰啉-5,6-二酮(phon)与二水合氯化铜反应得到了超分子配合物[Cu2(phon)2(μ2-Cl)2Cl2].DMF(1),并通过X射线单晶衍射、元素分析、红外光谱和紫外-可见光谱对它进行了表征。结果表明,配合物1中铜离子处于畸变的四方锥配位构...利用1,10-邻菲啰啉-5,6-二酮(phon)与二水合氯化铜反应得到了超分子配合物[Cu2(phon)2(μ2-Cl)2Cl2].DMF(1),并通过X射线单晶衍射、元素分析、红外光谱和紫外-可见光谱对它进行了表征。结果表明,配合物1中铜离子处于畸变的四方锥配位构型中,分子间通过C—H…Cl and C—H…O氢键和π-π堆积作用形成二维网络超分子结构。展开更多
A novel μ-S-bridged di-palladium(Ⅱ) complex, {[(phen)Pd( μ-SPr)2Pd(phen)](NO3)2·2H2O} (1) was synthesized and characterized by the 1H NMR, element analysis and single crystal X-ray diffraction. It crystallizes...A novel μ-S-bridged di-palladium(Ⅱ) complex, {[(phen)Pd( μ-SPr)2Pd(phen)](NO3)2·2H2O} (1) was synthesized and characterized by the 1H NMR, element analysis and single crystal X-ray diffraction. It crystallizes in the monoclinic space group C2/c with unit cell parameters: a=2.165 1(3) nm, b=1.291 4(2) nm, c=2.716 2(3) nm, β=111.987(3)°, and V=7.041 8(16) nm3, Z=8, R=0.054 4, wR=0.127 4. The X-ray crystal structure analysis revealed that two 1,10-phenanthroline palladium(Ⅱ) moieties were bridged by two n-propylmercapatan molecules in coplanar fashion with the dimensions of 1.55 nm × 0.88 nm. The plane-to-plane distance of the complex 1 is 0.33 nm, which reveals strong aromatic-aromatic π-π interaction. CCDC: 292998.展开更多
We synthesized oligo（p-phenyleneethynylene）s and oligo（p-phenyleneethynylene）s end-capped by vinyl by Sonogashira cross-coupling reaction. Then we prepared cross-linked PPE with or without residue vinyl by radical...We synthesized oligo（p-phenyleneethynylene）s and oligo（p-phenyleneethynylene）s end-capped by vinyl by Sonogashira cross-coupling reaction. Then we prepared cross-linked PPE with or without residue vinyl by radical polymerization or heat curing at 175280 ℃ of vinyl-functionalized olgomers. Having investigated cross-linked PPE and oligomers by FTIR, WXRD and photoluminescence, we found that cross-linked PPE without residual vinyl destroys the main chain π-π stacking completely in solid state. Moreover, the wavelength of the strongest emission of these cross-linked PPE varies from 310 nm to 390 nm, so they can be used as purple/blue light-emitting materials.展开更多
A novel cadmium(Ⅱ) isothiocyanate complex [Cd(N-MeIM)2(SCN)2]n (N-MeIM=N-methylimidazole) has been prepared and characterized by spectroscopic analysis and crystallographic method. The title compound crystallize in t...A novel cadmium(Ⅱ) isothiocyanate complex [Cd(N-MeIM)2(SCN)2]n (N-MeIM=N-methylimidazole) has been prepared and characterized by spectroscopic analysis and crystallographic method. The title compound crystallize in the Triclinic system, space group P1, with lattice parameters a=0.589 50(12) nm, b=0.785 70(16) nm, c=0.882 00(18) nm, α=110.98(3)°, β=106.49(3)°, γ=95.08(3)°, and Z=1. The title compound exhibits an infinite chain structure in which each pair of Cd atoms is bridged by two η-1,3-SCN- groups. The unique Cd atom lies on an inversion centre and the coordination sphere is completed by two N-MeIM N atoms to form a CdS2N4 octahedron. The polymeric chains are further extended into three-dimensional network via π...π stackings interactions between the imidazole rings. The cyclic voltammetry behaviors of the compound on glass carbon electrode showed a typical irreversible process. CCDC: 265283.展开更多
The title complex was synthesized by reaction of 2,2′-bipyridine(bipy) and zinc sulfate heptahrdrate in water-methanol solution.The crystal structure was determined by elemental analysis and X-ray diffraction.The res...The title complex was synthesized by reaction of 2,2′-bipyridine(bipy) and zinc sulfate heptahrdrate in water-methanol solution.The crystal structure was determined by elemental analysis and X-ray diffraction.The results show that the title complex belongs to monoclinic system with space group Cc and cell parameter: a = 1.5420(2) nm,b = 1.2696(2) nm,c = 0.6704(1) nm.β= 102.178(2)°.V = 1.2830(3) nm3,Z = 4,Dc = 1.831 g/cm3,μ= 2.104 mm-1,F(000) = 720.The Zn(Ⅱ) is coordinated by one bipy,two water molecules and one SO42-.At the same time,the Zn(Ⅱ) formed a distorted tetrasquare pyramid structure.The complex formed 1D straight chain by SO42-anion,and 1D chain assembled into double-stranded chain by π-π stacking interactions(ca:0.335(1) nm),furthmore,double-stranded chain extended to 2D network by O-H…O hrdrogen bonds,2D network constructed 3D supramolecular structure by C-H…O hrdrogen bonds.展开更多
用水杨酸和吡啶与Ni(ClO4)26H2O 合成了一个新颖配位聚合物[Ni(Hsal)2(Py)2]n。对配合物进行了X射线衍射结构表征, C24H20N2NiO6, Mr = 491.13, 晶体属三斜晶系, P 空间群, 晶胞参数: a = 7.372(2), b =10.852(2), c = 14.728(3) ? a = ...用水杨酸和吡啶与Ni(ClO4)26H2O 合成了一个新颖配位聚合物[Ni(Hsal)2(Py)2]n。对配合物进行了X射线衍射结构表征, C24H20N2NiO6, Mr = 491.13, 晶体属三斜晶系, P 空间群, 晶胞参数: a = 7.372(2), b =10.852(2), c = 14.728(3) ? a = 108.36(3), b = 93.83(3), g = 103.67(3), V = 1073.7(4) ?。F(000) = 508, m = 0.949mm-1, Z = 2, Dc = 1.519 g/cm3。最后修正到R = 0.0390, wR = 0.0772。配合物中Ni为五配位, 呈四方锥构型。配合物中2个水杨酸根的配位方式不一样, 其中一个水杨酸根作为双齿桥连配体, 使配合物呈一维链状结构。水杨酸苯环的-堆积作用和分子间的氢键作用, 又使配合物呈二维网络结构。展开更多
文摘Aggregation behavior of 5,10,15-tris(pentafluorophenyl)corrole (F15TPC), 5,10,15,20-tetra(pentafluoroph-enyl)porphyrin (F20TPP), and their copper complexes in DCM solution were investigated by using UV-Vis spectro-scopic method. F20TPP and F20TPPCu exhibited strong π-π stacking interactions in DCM, and the intermolecular dimerization constants turned out to be 1.82 × 103 and 17.2 × 103 L·mol-1 respectively. However, extinction coefficients of F15TPC and F15TPCCu at soret band remained unchanged with increasing in their concentrations from 1.0 to 40.0 μmol·L-1, indicating they remained monomeric in DCM solution. Based on DFT calculation and the π-π stacking geometries observed in crystal structures of metal octaethylcorrole complexes, destroy of π-π interactions in F15TPC and F15TPCCu may be understood by the electrostatic potential surfaces (EPS) features of the molecules and steric repulsions caused by the introducing of three phenyl at the meso- positions of corrole macrocycle.
文摘利用1,10-邻菲啰啉-5,6-二酮(phon)与二水合氯化铜反应得到了超分子配合物[Cu2(phon)2(μ2-Cl)2Cl2].DMF(1),并通过X射线单晶衍射、元素分析、红外光谱和紫外-可见光谱对它进行了表征。结果表明,配合物1中铜离子处于畸变的四方锥配位构型中,分子间通过C—H…Cl and C—H…O氢键和π-π堆积作用形成二维网络超分子结构。
文摘A novel μ-S-bridged di-palladium(Ⅱ) complex, {[(phen)Pd( μ-SPr)2Pd(phen)](NO3)2·2H2O} (1) was synthesized and characterized by the 1H NMR, element analysis and single crystal X-ray diffraction. It crystallizes in the monoclinic space group C2/c with unit cell parameters: a=2.165 1(3) nm, b=1.291 4(2) nm, c=2.716 2(3) nm, β=111.987(3)°, and V=7.041 8(16) nm3, Z=8, R=0.054 4, wR=0.127 4. The X-ray crystal structure analysis revealed that two 1,10-phenanthroline palladium(Ⅱ) moieties were bridged by two n-propylmercapatan molecules in coplanar fashion with the dimensions of 1.55 nm × 0.88 nm. The plane-to-plane distance of the complex 1 is 0.33 nm, which reveals strong aromatic-aromatic π-π interaction. CCDC: 292998.
文摘We synthesized oligo（p-phenyleneethynylene）s and oligo（p-phenyleneethynylene）s end-capped by vinyl by Sonogashira cross-coupling reaction. Then we prepared cross-linked PPE with or without residue vinyl by radical polymerization or heat curing at 175280 ℃ of vinyl-functionalized olgomers. Having investigated cross-linked PPE and oligomers by FTIR, WXRD and photoluminescence, we found that cross-linked PPE without residual vinyl destroys the main chain π-π stacking completely in solid state. Moreover, the wavelength of the strongest emission of these cross-linked PPE varies from 310 nm to 390 nm, so they can be used as purple/blue light-emitting materials.
基金Supported by the National Natural Science Foundation of China(21171119,11574408,81573822,21376008)the Beijing Natural Science Foundation(2172017)+1 种基金the Fundamental Research Funds for the Central Universities in China University of Geosciences(2-9-2021-008)the R&D Program of Beijing Municipal Education Commission(KM202210028015)。
文摘A novel cadmium(Ⅱ) isothiocyanate complex [Cd(N-MeIM)2(SCN)2]n (N-MeIM=N-methylimidazole) has been prepared and characterized by spectroscopic analysis and crystallographic method. The title compound crystallize in the Triclinic system, space group P1, with lattice parameters a=0.589 50(12) nm, b=0.785 70(16) nm, c=0.882 00(18) nm, α=110.98(3)°, β=106.49(3)°, γ=95.08(3)°, and Z=1. The title compound exhibits an infinite chain structure in which each pair of Cd atoms is bridged by two η-1,3-SCN- groups. The unique Cd atom lies on an inversion centre and the coordination sphere is completed by two N-MeIM N atoms to form a CdS2N4 octahedron. The polymeric chains are further extended into three-dimensional network via π...π stackings interactions between the imidazole rings. The cyclic voltammetry behaviors of the compound on glass carbon electrode showed a typical irreversible process. CCDC: 265283.
文摘The title complex was synthesized by reaction of 2,2′-bipyridine(bipy) and zinc sulfate heptahrdrate in water-methanol solution.The crystal structure was determined by elemental analysis and X-ray diffraction.The results show that the title complex belongs to monoclinic system with space group Cc and cell parameter: a = 1.5420(2) nm,b = 1.2696(2) nm,c = 0.6704(1) nm.β= 102.178(2)°.V = 1.2830(3) nm3,Z = 4,Dc = 1.831 g/cm3,μ= 2.104 mm-1,F(000) = 720.The Zn(Ⅱ) is coordinated by one bipy,two water molecules and one SO42-.At the same time,the Zn(Ⅱ) formed a distorted tetrasquare pyramid structure.The complex formed 1D straight chain by SO42-anion,and 1D chain assembled into double-stranded chain by π-π stacking interactions(ca:0.335(1) nm),furthmore,double-stranded chain extended to 2D network by O-H…O hrdrogen bonds,2D network constructed 3D supramolecular structure by C-H…O hrdrogen bonds.
文摘用水杨酸和吡啶与Ni(ClO4)26H2O 合成了一个新颖配位聚合物[Ni(Hsal)2(Py)2]n。对配合物进行了X射线衍射结构表征, C24H20N2NiO6, Mr = 491.13, 晶体属三斜晶系, P 空间群, 晶胞参数: a = 7.372(2), b =10.852(2), c = 14.728(3) ? a = 108.36(3), b = 93.83(3), g = 103.67(3), V = 1073.7(4) ?。F(000) = 508, m = 0.949mm-1, Z = 2, Dc = 1.519 g/cm3。最后修正到R = 0.0390, wR = 0.0772。配合物中Ni为五配位, 呈四方锥构型。配合物中2个水杨酸根的配位方式不一样, 其中一个水杨酸根作为双齿桥连配体, 使配合物呈一维链状结构。水杨酸苯环的-堆积作用和分子间的氢键作用, 又使配合物呈二维网络结构。
