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2016 Volume 35 Issue 5
2016, 35(5): 669-678
doi: 10.14102/j.cnki.0254-5861.2011-1097
Abstract:
Periodic density functional theory calculations have been performed to investigate the chemisorption behavior of CO2 molecule on a series of surface alloys that are built by dispersing individual middle-late transition metal (TM) atoms (TM = Fe, Co, Ni, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au) on the Cu(100) and Cu(111) surfaces. The most stable configurations of CO2 chemisorbed on different TM/Cu surfaces are determined, and the results show that among the late transition metals, Co, Ru, and Os are potentially good dopants to enhance the chemisorption and activation of CO2 on copper surfaces. To obtain a deep understanding of the adsorption property, the bonding characteristics of the adsorption bonds are carefully examined by the crystal orbital Hamilton population technique, which reveals that the TM atom primarily provides d orbitals with z-component, namely dz2, dxz, and dyz orbitals to interact with the adsorbate.
Periodic density functional theory calculations have been performed to investigate the chemisorption behavior of CO2 molecule on a series of surface alloys that are built by dispersing individual middle-late transition metal (TM) atoms (TM = Fe, Co, Ni, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au) on the Cu(100) and Cu(111) surfaces. The most stable configurations of CO2 chemisorbed on different TM/Cu surfaces are determined, and the results show that among the late transition metals, Co, Ru, and Os are potentially good dopants to enhance the chemisorption and activation of CO2 on copper surfaces. To obtain a deep understanding of the adsorption property, the bonding characteristics of the adsorption bonds are carefully examined by the crystal orbital Hamilton population technique, which reveals that the TM atom primarily provides d orbitals with z-component, namely dz2, dxz, and dyz orbitals to interact with the adsorbate.
2016, 35(5): 679-686
doi: 10.14102/j.cnki.0254-5861.2011-0944
Abstract:
A Schiff base DSH DSH = 4-dipropylanilino-styryl hydrazine has been synthe-sized and fully characterized by 1H NMR, 13C NMR, ESI-MS, elemental analysis and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1 , with a = 8.4475, b = 10.5435, c = 14.5405 Å, α = 78.6005, β = 78.2225, γ = 78.2475°, V = 12251 Å3. , Z = 2, Dc = 1.103 g/m3. , F000 = 444, Mr = 406.60, μ = 0.066 mm-1. , the final R = 0.0414 and wR = 0.1065 for 8691 observed reflections with I > 2I. The structural analysis revealed that the molecule possesses good planar structure. The absorption spectra and one-photon fluorescence in different solvents were experimentally studied. The result indicates that the compound exhibits intense fluorescent emission bands in protic solvents, such as ethanol and methanol. Quantum chemical calculations based on time-dependent density functional theory TD-DFT at the level of TD-DFT/B3LYP/6-31G were performed to investigate the UV absorption spectrum, and influence of solvents on the fluorescence spectra is analyzed based on the optimized structure at the level of B3LYP/6-31Gd.
A Schiff base DSH DSH = 4-dipropylanilino-styryl hydrazine has been synthe-sized and fully characterized by 1H NMR, 13C NMR, ESI-MS, elemental analysis and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1 , with a = 8.4475, b = 10.5435, c = 14.5405 Å, α = 78.6005, β = 78.2225, γ = 78.2475°, V = 12251 Å3. , Z = 2, Dc = 1.103 g/m3. , F000 = 444, Mr = 406.60, μ = 0.066 mm-1. , the final R = 0.0414 and wR = 0.1065 for 8691 observed reflections with I > 2I. The structural analysis revealed that the molecule possesses good planar structure. The absorption spectra and one-photon fluorescence in different solvents were experimentally studied. The result indicates that the compound exhibits intense fluorescent emission bands in protic solvents, such as ethanol and methanol. Quantum chemical calculations based on time-dependent density functional theory TD-DFT at the level of TD-DFT/B3LYP/6-31G were performed to investigate the UV absorption spectrum, and influence of solvents on the fluorescence spectra is analyzed based on the optimized structure at the level of B3LYP/6-31Gd.
2016, 35(5): 687-697
doi: 10.14102/j.cnki.0254-5861.2011-0803
Abstract:
Exploring, designing, and synthesizing novel organic field-effect transistor (OFET) materials have kept an important and hot issue in organic electronics. In the current work, the charge transport properties for 2,5-di(cyanovinyl)thiophene/furan crystal associating two pentafluorophenyl units linked via the azomethine bond, CTE and CFE have been theoretically investigated by means of density functional theory (DFT) calculations coupled with the incoherent charge-hopping mechanism and the kinetic Monte Carlo simulation. Results show that these two compounds possess remarkably low-lying HOMO (–7.0 eV) and LUMO (–4.0 eV) levels, as well as large electron affinities (> 3.0 eV), which indicate their high stability exposed to air as promising OFET materials. However, the µh value at room temperature (T = 300 K) is predicted to be 2.058×10-7 cm2·V-1·s-1, and the µe is as low as 9.834×10-8 cm2·V-1·s-1 for CFT crystal. Meanwhile, these two values are 7.561 × 10-8 and 8.437 × 10-8 cm2·V-1·s-1 for the CFE crystal, respectively. Furthermore, the simulation of angle-dependent mobility in the a-b, a-c, and b-c crystal planes shows that the charge transport in CTE and CFE crystals is remarkably anisotropic, which maybe is helpful for the fabrication of high-performance OFET devices.
Exploring, designing, and synthesizing novel organic field-effect transistor (OFET) materials have kept an important and hot issue in organic electronics. In the current work, the charge transport properties for 2,5-di(cyanovinyl)thiophene/furan crystal associating two pentafluorophenyl units linked via the azomethine bond, CTE and CFE have been theoretically investigated by means of density functional theory (DFT) calculations coupled with the incoherent charge-hopping mechanism and the kinetic Monte Carlo simulation. Results show that these two compounds possess remarkably low-lying HOMO (–7.0 eV) and LUMO (–4.0 eV) levels, as well as large electron affinities (> 3.0 eV), which indicate their high stability exposed to air as promising OFET materials. However, the µh value at room temperature (T = 300 K) is predicted to be 2.058×10-7 cm2·V-1·s-1, and the µe is as low as 9.834×10-8 cm2·V-1·s-1 for CFT crystal. Meanwhile, these two values are 7.561 × 10-8 and 8.437 × 10-8 cm2·V-1·s-1 for the CFE crystal, respectively. Furthermore, the simulation of angle-dependent mobility in the a-b, a-c, and b-c crystal planes shows that the charge transport in CTE and CFE crystals is remarkably anisotropic, which maybe is helpful for the fabrication of high-performance OFET devices.
2016, 35(5): 698-704
doi: 10.14102/j.cnki.0254-5861.2011-1100
Abstract:
A series of acridine-1,2,3-triazole derivatives were designed, synthesized and characterized by NMR. 1-(2-methylacridinyl)-4-(4-methyl phenyl)-1,2,3-triazole (4f), C23H18N4, was structurally determined by single-crystal X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a = 9.585(4), b = 9.684(4), c = 11.339(5) Å, β = 88.250(7)°, V = 925.3(6), Z = 2, Dc= 1.258 g/cm3, F(000) = 368, μ = 0.077 mm-1, the final R = 0.0808 and wR = 0.2218 for 3386 observed reflections (I > 2σ(I)). X-ray analysis indicates that the acridine ring is almost vertical to triazole ring with the dihedral angle nearly to be 75°. The crystal packing of the compound is stabilized mainly by π-π interaction. The preliminary biological tests display that some of the title compounds possess a good anti-tumour activity against MGC-803 and T24.
A series of acridine-1,2,3-triazole derivatives were designed, synthesized and characterized by NMR. 1-(2-methylacridinyl)-4-(4-methyl phenyl)-1,2,3-triazole (4f), C23H18N4, was structurally determined by single-crystal X-ray diffraction. It crystallizes in the triclinic system, space group P1 with a = 9.585(4), b = 9.684(4), c = 11.339(5) Å, β = 88.250(7)°, V = 925.3(6), Z = 2, Dc= 1.258 g/cm3, F(000) = 368, μ = 0.077 mm-1, the final R = 0.0808 and wR = 0.2218 for 3386 observed reflections (I > 2σ(I)). X-ray analysis indicates that the acridine ring is almost vertical to triazole ring with the dihedral angle nearly to be 75°. The crystal packing of the compound is stabilized mainly by π-π interaction. The preliminary biological tests display that some of the title compounds possess a good anti-tumour activity against MGC-803 and T24.
2016, 35(5): 705-712
doi: 10.14102/j.cnki.0254-5861.2011-1055
Abstract:
A novel {[bis(pyridine-kN)bis(3,5-dinitrosalicylato k-O,O')Zn(II)][bis(pyridine-kN)Zn(II)]} (C34H24N8O14Zn2) was synthesized by a self-assemble method at room temperature. The molecular structure was determined by single-crystal X-ray analysis. The compound crystallizes in the monoclinic system, space group P21/n with a = 12.2156, b = 13.5696, c = 22.5602 Å, β = 90.061°, Z = 4 and V = 3739.6(3) Å3. The new 1D binuclear coordination polymer {[bis(py-kN)bis(3,5-dinitrosal k-O,O¢) Zn(II)][bis(py-kN)Zn(II)]} resulted from two different types of moieties. The polymer[bis(py-kN)bis(3,5-dinitrosal k-O,O')Zn(II)] unit is connected with [bis(py-kN) Zn(II)] by zigzag topology. One zinc(II) cation has a six-fold coordination environment, in which the metal atom is connected with four oxygen atoms of two 3,5-dinitrosalicylic acids to form equatorial bonds and two nitrogen atoms of pyridine to generate the axial bonds. Other four-fold nucleus contain two Zn–O bonds from different 3,5-dinitrosalicylic acids and two bonds with the N-atom of pyridine. Antimicrobial assay results indicated that the compound showed moderate activities against different bacterial and fungal strains.
A novel {[bis(pyridine-kN)bis(3,5-dinitrosalicylato k-O,O')Zn(II)][bis(pyridine-kN)Zn(II)]} (C34H24N8O14Zn2) was synthesized by a self-assemble method at room temperature. The molecular structure was determined by single-crystal X-ray analysis. The compound crystallizes in the monoclinic system, space group P21/n with a = 12.2156, b = 13.5696, c = 22.5602 Å, β = 90.061°, Z = 4 and V = 3739.6(3) Å3. The new 1D binuclear coordination polymer {[bis(py-kN)bis(3,5-dinitrosal k-O,O¢) Zn(II)][bis(py-kN)Zn(II)]} resulted from two different types of moieties. The polymer[bis(py-kN)bis(3,5-dinitrosal k-O,O')Zn(II)] unit is connected with [bis(py-kN) Zn(II)] by zigzag topology. One zinc(II) cation has a six-fold coordination environment, in which the metal atom is connected with four oxygen atoms of two 3,5-dinitrosalicylic acids to form equatorial bonds and two nitrogen atoms of pyridine to generate the axial bonds. Other four-fold nucleus contain two Zn–O bonds from different 3,5-dinitrosalicylic acids and two bonds with the N-atom of pyridine. Antimicrobial assay results indicated that the compound showed moderate activities against different bacterial and fungal strains.
2016, 35(5): 713-717
doi: 10.14102/j.cnki.0254-5861.2011-0955
Abstract:
A new ternary neodymium zirconium sulfide Nd2ZrS5 was synthesized by high-temperature solid-state reaction and structurally characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic space group Pnma (No. 62) belonging to the Y2HfS5 structure-type with a = 11.461(4), b = 8.009(3), c = 7.315(3) Å, Z = 2 and V = 671.5(4) Å3. Its structure features NdS8 and ZrS7 polyhedra-constructed a 3-D network. The data of magnetic susceptibility indicate its antiferromagnetic-like behavior without magnetic order down to 2 K.
A new ternary neodymium zirconium sulfide Nd2ZrS5 was synthesized by high-temperature solid-state reaction and structurally characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic space group Pnma (No. 62) belonging to the Y2HfS5 structure-type with a = 11.461(4), b = 8.009(3), c = 7.315(3) Å, Z = 2 and V = 671.5(4) Å3. Its structure features NdS8 and ZrS7 polyhedra-constructed a 3-D network. The data of magnetic susceptibility indicate its antiferromagnetic-like behavior without magnetic order down to 2 K.
2016, 35(5): 718-724
doi: 10.14102/j.cnki.0254-5861.2011-0919
Abstract:
A convenient method of synthesizing a tripeptide-containing N-methyl group amino acid was developed using O-benzotriazole-N,N,N',N'-tetramethyluronium-hexafluorophosphate as the condensing agent. The crystals of tripeptide had white needles belonging to the orthorhombic space group P212121. The conformational preference for homochiral tripeptides with one N-methylated amide bond was also investigated. Crystal-structure analysis showed that homochiral tripeptides with an internal N-methylated amide bond preferred a trans-amide form, thereby giving the peptide b-fold characteristics. Intermolecular C–H…O and N–H…O hydrogen bonds linked the molecules into a one-dimensional chain and stabilized the structure.
A convenient method of synthesizing a tripeptide-containing N-methyl group amino acid was developed using O-benzotriazole-N,N,N',N'-tetramethyluronium-hexafluorophosphate as the condensing agent. The crystals of tripeptide had white needles belonging to the orthorhombic space group P212121. The conformational preference for homochiral tripeptides with one N-methylated amide bond was also investigated. Crystal-structure analysis showed that homochiral tripeptides with an internal N-methylated amide bond preferred a trans-amide form, thereby giving the peptide b-fold characteristics. Intermolecular C–H…O and N–H…O hydrogen bonds linked the molecules into a one-dimensional chain and stabilized the structure.
2016, 35(5): 725-730
doi: 10.14102/j.cnki.0254-5861.2011-0923
Abstract:
The title complex bis{4-chloro-2-[(6-methyl-pyridin-2-ylimino)-methyl]-phenol}-palladium(II) (C26H20Cl2N4O2Pd) has been synthesized by the reaction of 4-chloro-2-[(6-methyl-pyridin-2-ylimino)-methyl]-phenol with Pd(CH3COO)2, and characterized by IR spectrum and elemental analysis. Single-crystal X-ray diffraction analysis results further confirmed the molecular structures. The crystal belongs to the monoclinic system, space group P21/c with a = 4.1324(2), b = 23.5432(16), c = 11.8943(8) Å, β = 91.238(5)°, V = 1156.93(12) Å3, C26H20Cl2N4O2Pd, Mr = 597.76, Z = 2, Dc = 1.716 g/cm3, μ = 1.067 mm-1, F(000) = 600, the final R = 0.0247 and wR = 0.0677 (I > 2s(I)). In the presence of methylaluminoxane (MAO), the complex exhibits excellent catalytic activities (1.737×107 g of PNB (mol of Pd)-1×h-1) in the vinyl polymerization of norbornene.
The title complex bis{4-chloro-2-[(6-methyl-pyridin-2-ylimino)-methyl]-phenol}-palladium(II) (C26H20Cl2N4O2Pd) has been synthesized by the reaction of 4-chloro-2-[(6-methyl-pyridin-2-ylimino)-methyl]-phenol with Pd(CH3COO)2, and characterized by IR spectrum and elemental analysis. Single-crystal X-ray diffraction analysis results further confirmed the molecular structures. The crystal belongs to the monoclinic system, space group P21/c with a = 4.1324(2), b = 23.5432(16), c = 11.8943(8) Å, β = 91.238(5)°, V = 1156.93(12) Å3, C26H20Cl2N4O2Pd, Mr = 597.76, Z = 2, Dc = 1.716 g/cm3, μ = 1.067 mm-1, F(000) = 600, the final R = 0.0247 and wR = 0.0677 (I > 2s(I)). In the presence of methylaluminoxane (MAO), the complex exhibits excellent catalytic activities (1.737×107 g of PNB (mol of Pd)-1×h-1) in the vinyl polymerization of norbornene.
2016, 35(5): 731-739
doi: 10.14102/j.cnki.0254-5861.2011-0918
Abstract:
We use the ab initio density functional theory to calculate the band structure, den-sity of states, charge transfer, charge density difference, binding energy and vibration frequency. We can see that the conduction band through the Fermi level include SWNT/H2/Li, SWNT/H2/Al and SWNT/H2/Ca, which shows a kind of metallic character. The charge distribution and contour plots of charge difference density of ion/H2/SWNT show charge transfer between ion and H2 molecules rather than between H2 and H2. Meanwhile, the interaction between Al, Ca and H2 is weaker than that of Li. We can also prove that the ion is the primary reason to the increase of adsorption energy of hydrogen molecule in SWNT. Finally, we calculate the vibration frequency and don’t find any imaginary frequency, which proves that the (7,0) SWNT is more stable.
We use the ab initio density functional theory to calculate the band structure, den-sity of states, charge transfer, charge density difference, binding energy and vibration frequency. We can see that the conduction band through the Fermi level include SWNT/H2/Li, SWNT/H2/Al and SWNT/H2/Ca, which shows a kind of metallic character. The charge distribution and contour plots of charge difference density of ion/H2/SWNT show charge transfer between ion and H2 molecules rather than between H2 and H2. Meanwhile, the interaction between Al, Ca and H2 is weaker than that of Li. We can also prove that the ion is the primary reason to the increase of adsorption energy of hydrogen molecule in SWNT. Finally, we calculate the vibration frequency and don’t find any imaginary frequency, which proves that the (7,0) SWNT is more stable.
2016, 35(5): 740-746
doi: 10.14102/j.cnki.0254-5861.2011-0972
Abstract:
Two new Cu(I) complexes [CuCl(3-PyOH)(PPh3)2] (1) and [Cu2(μ-Cl)2(4-Stpy)(Ph3P)3] (2) (PyOH = hydroxypyridine; stpy = styrylpyridine) with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P21/c with a = 9.8945(7), b = 37.266(2), c = 10.9461(7) Å, β = 116.0750(10)°, V = 3625.3(4) Å3, Z = 4, Dc = 1.350 Mg/cm-3, μ = 0.801 mm-1, F(000) = 1528, the final R = 0.0320 and wR= 0.0729 for 18568 observed reflections (I> 2s(I)), R(all data) = 0.0413, wR(all data) = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.290(3), b = 20.388(5), c = 24.092(6) Å, β = 102.028(4)°, V = 5424(2) Å3, Z = 4, Dc = 1.428 Mg/cm-3, μ = 1.016 mm-1, F(000) = 2408, the final R = 0.0568 and wR= 0.1486 for 27644 observed reflections (I> 2s(I)), R(all data) = 0.0716, wR(all data) = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu(I) complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.
Two new Cu(I) complexes [CuCl(3-PyOH)(PPh3)2] (1) and [Cu2(μ-Cl)2(4-Stpy)(Ph3P)3] (2) (PyOH = hydroxypyridine; stpy = styrylpyridine) with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P21/c with a = 9.8945(7), b = 37.266(2), c = 10.9461(7) Å, β = 116.0750(10)°, V = 3625.3(4) Å3, Z = 4, Dc = 1.350 Mg/cm-3, μ = 0.801 mm-1, F(000) = 1528, the final R = 0.0320 and wR= 0.0729 for 18568 observed reflections (I> 2s(I)), R(all data) = 0.0413, wR(all data) = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.290(3), b = 20.388(5), c = 24.092(6) Å, β = 102.028(4)°, V = 5424(2) Å3, Z = 4, Dc = 1.428 Mg/cm-3, μ = 1.016 mm-1, F(000) = 2408, the final R = 0.0568 and wR= 0.1486 for 27644 observed reflections (I> 2s(I)), R(all data) = 0.0716, wR(all data) = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu(I) complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.
2016, 35(5): 747-752
doi: 10.14102/j.cnki.0254-5861.2011-0916
Abstract:
Reaction of a tripodal ligand, N,N',N"-tris(3-pyridinyl) phosphoric trimide (TPPA) and CuBr2·2H2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964(5), b = 10.2592, c = 10.5822(8) Å, V = 933.01(9) Å3, Z = 2, C30H24Br4Cu3N12O2P2, Mr = 985.02, Dc = 1.753 g/cm3, F(000) = 4072 and μ(MoKα) = 0.746 mm-1. The final R and wR are 0.0588 and 0.1329 for 4260 observed reflections with I> 2s(I). Cu(I) is tetrahedrally coordinated and Cu(II) center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N–H…O and N–H…Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.
Reaction of a tripodal ligand, N,N',N"-tris(3-pyridinyl) phosphoric trimide (TPPA) and CuBr2·2H2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964(5), b = 10.2592, c = 10.5822(8) Å, V = 933.01(9) Å3, Z = 2, C30H24Br4Cu3N12O2P2, Mr = 985.02, Dc = 1.753 g/cm3, F(000) = 4072 and μ(MoKα) = 0.746 mm-1. The final R and wR are 0.0588 and 0.1329 for 4260 observed reflections with I> 2s(I). Cu(I) is tetrahedrally coordinated and Cu(II) center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N–H…O and N–H…Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.
2016, 35(5): 753-757
doi: 10.14102/j.cnki.0254-5861.2011-0958
Abstract:
A new Pb(II) coordination polymer, [Pb(1,4-chdc)(L)]n·nH2O (1), was synthesized under hydrothermal condition (1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid and L = 2-(3-fluoro-phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline). Its crystal structure was determined by single-crystal X-ray diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 9.1182(8), b = 11.3249(10), c = 12.7326(12) Å, α = 77.897(2), β = 81.644(2), γ = 84.491(2)°, V = 1269.0(2) Å3, Z = 2, C27H24FN4O5Pb, Mr = 710.69, Dc = 1.860 g/cm3, F(000) = 690, μ(MoKa) = 6.701 mm-1, R = 0.0349 and wR = 0.0746. In 1, each 1,4-chdc anion bridges two neighboring Pb(II) atoms in a bidentate chelating coordination mode to give a chain structure. The L ligands are attached on one side of the chain through chelating the Pb(II) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. The O–H…O and N–H…O hydrogen bonding interactions further stabilize the supramolecular layer structure of 1. Moreover, solid state luminescent property of 1 was also studied.
A new Pb(II) coordination polymer, [Pb(1,4-chdc)(L)]n·nH2O (1), was synthesized under hydrothermal condition (1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid and L = 2-(3-fluoro-phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline). Its crystal structure was determined by single-crystal X-ray diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 9.1182(8), b = 11.3249(10), c = 12.7326(12) Å, α = 77.897(2), β = 81.644(2), γ = 84.491(2)°, V = 1269.0(2) Å3, Z = 2, C27H24FN4O5Pb, Mr = 710.69, Dc = 1.860 g/cm3, F(000) = 690, μ(MoKa) = 6.701 mm-1, R = 0.0349 and wR = 0.0746. In 1, each 1,4-chdc anion bridges two neighboring Pb(II) atoms in a bidentate chelating coordination mode to give a chain structure. The L ligands are attached on one side of the chain through chelating the Pb(II) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. The O–H…O and N–H…O hydrogen bonding interactions further stabilize the supramolecular layer structure of 1. Moreover, solid state luminescent property of 1 was also studied.
2016, 35(5): 758-764
doi: 10.14102/j.cnki.0254-5861.2011-0938
Abstract:
A unique metal-organic framework (MOF) [Eu2(L)3(phen)2]n (1, H2L = 4,6-diben-zoylisophthalic acid, phen = 1,10-phenanthroline) has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray analysis, elemental analyses, powder X-ray diffraction, TGA measurement as well as IR spectra. The crystal is of triclinic system, space group P , C90H52Eu2N4O18, Mr = 1781.32, a = 9.8697(4), b = 16.7466(6), c = 22.2556(10) Å, α = 87.113(3), β = 77.575(5), γ = 89.458(3)°, V = 3587.8(3) Å3, Z = 2, Dc = 1.649 g/cm3, F(000) = 1780, μ(MoKa) = 1.813 mm-1, Rint = 0.0181, R = 0.0260 and wR = 0.0592 for 14000 observed reflections with I> 2σ(I). X-ray analysis shows that the title compound exhibits a 2D layer structure linked by L ligands with two coordination modes and two distinguished conformations, and further linked into a 3D supramolecular architecture through C–H…O weak interactions between hydrogen of phen phenyl ring and the carboxylate oxygen atom of adjacent sheets. In addition, the luminescence property of 1 was investigated.
A unique metal-organic framework (MOF) [Eu2(L)3(phen)2]n (1, H2L = 4,6-diben-zoylisophthalic acid, phen = 1,10-phenanthroline) has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray analysis, elemental analyses, powder X-ray diffraction, TGA measurement as well as IR spectra. The crystal is of triclinic system, space group P , C90H52Eu2N4O18, Mr = 1781.32, a = 9.8697(4), b = 16.7466(6), c = 22.2556(10) Å, α = 87.113(3), β = 77.575(5), γ = 89.458(3)°, V = 3587.8(3) Å3, Z = 2, Dc = 1.649 g/cm3, F(000) = 1780, μ(MoKa) = 1.813 mm-1, Rint = 0.0181, R = 0.0260 and wR = 0.0592 for 14000 observed reflections with I> 2σ(I). X-ray analysis shows that the title compound exhibits a 2D layer structure linked by L ligands with two coordination modes and two distinguished conformations, and further linked into a 3D supramolecular architecture through C–H…O weak interactions between hydrogen of phen phenyl ring and the carboxylate oxygen atom of adjacent sheets. In addition, the luminescence property of 1 was investigated.
2016, 35(5): 765-773
doi: 10.14102/j.cnki.0254-5861.2011-0934
Abstract:
Two new coordination polymers containing rigid bis(triazole), namely, [Ni(btb)0.5(nph)(H2O)]n (1) and [Zn(btb)(SO4)]n (2) (btb = 4,4'-bis(1,2,4-triazolyl-1-yl)-biphenyl, H2nph = 3-nitrophthalic acid) have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal (3,4,4)-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C–H…O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.
Two new coordination polymers containing rigid bis(triazole), namely, [Ni(btb)0.5(nph)(H2O)]n (1) and [Zn(btb)(SO4)]n (2) (btb = 4,4'-bis(1,2,4-triazolyl-1-yl)-biphenyl, H2nph = 3-nitrophthalic acid) have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal (3,4,4)-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C–H…O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.
2016, 35(5): 774-780
doi: 10.14102/j.cnki.0254-5861.2011-0956
Abstract:
By using "pillaring" strategy, a new Co(II)-MOF, [Co2(abtc)(bimb)2]·2H2O (1, H4abtc = 3,3',5,5'-azobenzenetetracarboxylic acid, bimb = 4,4'-bis(imidazole-1-ylmethyl)bi-phenyl), has been solvothermally synthesized and structurally characterized. The structural determination revealed that 1 features a 3D pillar-layered framework with (4,8)-connected {44.62}{48.620} topology based on dinuclear Co(II)-SBUs. The magnetic investigation shows that the dominant antiferromagnetic coupling is observed in compound 1.
By using "pillaring" strategy, a new Co(II)-MOF, [Co2(abtc)(bimb)2]·2H2O (1, H4abtc = 3,3',5,5'-azobenzenetetracarboxylic acid, bimb = 4,4'-bis(imidazole-1-ylmethyl)bi-phenyl), has been solvothermally synthesized and structurally characterized. The structural determination revealed that 1 features a 3D pillar-layered framework with (4,8)-connected {44.62}{48.620} topology based on dinuclear Co(II)-SBUs. The magnetic investigation shows that the dominant antiferromagnetic coupling is observed in compound 1.
2016, 35(5): 781-788
doi: 10.14102/j.cnki.0254-5861.2011-0951
Abstract:
Two new complexes, [Mn(L)(mmbda)(H2O)] (1) and [Co(L)(btc)(H2O)]·H2O (2), were synthesized by reacting the corresponding metal(II) salts with rigid ligand 1,4-di(1H-imidazol-4-yl)benzene (L) and two different carboxylic acids of 5-methylisophthalic acid (H2mmbda) and 1,2,4-benzenetricarboxylic acid (H3btc), respectively. The structures of the complexes were characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in triclinic, space group P with a = 6.9436(4), b = 9.7306(6), c = 15.5302(10) Å, α = 73.7430(10), β = 85.1010(10), γ = 70.0360(10)°, V = 946.75(10) Å3, Z = 2, C21H20N4O5Mn, Mr = 463.33, Dc = 1.618 g/cm3, μ = 0.742-1, S = 1.002, F(000) = 474, the final R = 0.0285 and wR = 0.0600 for 4328 observed reflections (I> 2σ(I)). Complex 2 crystallizes in monoclinic, space group P21/n with a = 12.5216(12), b = 7.3312(8), c = 22.510(2) Å, β = 93.104(2)°, V = 2063.3(4) Å3, Z = 4, C21H18N4O8Co, Mr = 513.31, Dc = 1.646 g/cm3, μ = 0.892 mm-1, S = 1.096, F(000) = 1044, the final R = 0.0673 and wR = 0.1780 for 3594 observed reflections (I> 2σ(I)). Both of complexes are one-dimensional (1D) chain structures and rich hydrogen bonds extend such 1D chains to form three-dimensional (3D) supramolecular polymers.
Two new complexes, [Mn(L)(mmbda)(H2O)] (1) and [Co(L)(btc)(H2O)]·H2O (2), were synthesized by reacting the corresponding metal(II) salts with rigid ligand 1,4-di(1H-imidazol-4-yl)benzene (L) and two different carboxylic acids of 5-methylisophthalic acid (H2mmbda) and 1,2,4-benzenetricarboxylic acid (H3btc), respectively. The structures of the complexes were characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in triclinic, space group P with a = 6.9436(4), b = 9.7306(6), c = 15.5302(10) Å, α = 73.7430(10), β = 85.1010(10), γ = 70.0360(10)°, V = 946.75(10) Å3, Z = 2, C21H20N4O5Mn, Mr = 463.33, Dc = 1.618 g/cm3, μ = 0.742-1, S = 1.002, F(000) = 474, the final R = 0.0285 and wR = 0.0600 for 4328 observed reflections (I> 2σ(I)). Complex 2 crystallizes in monoclinic, space group P21/n with a = 12.5216(12), b = 7.3312(8), c = 22.510(2) Å, β = 93.104(2)°, V = 2063.3(4) Å3, Z = 4, C21H18N4O8Co, Mr = 513.31, Dc = 1.646 g/cm3, μ = 0.892 mm-1, S = 1.096, F(000) = 1044, the final R = 0.0673 and wR = 0.1780 for 3594 observed reflections (I> 2σ(I)). Both of complexes are one-dimensional (1D) chain structures and rich hydrogen bonds extend such 1D chains to form three-dimensional (3D) supramolecular polymers.
2016, 35(5): 789-795
doi: 10.14102/j.cnki.0254-5861.2011-0933
Abstract:
The title complex bis{1-[[(3-methyl-pyridin-2-yl) amino] methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol} palladium (C42H56O2N4Pd) has been synthesized by the reaction of 1-[[(3-methyl-pyridin-2-yl)amino]methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol with Pd(OAc)2, and was characterized by IR and elemental analyses (C, H, N). Single-crystal X-ray diffraction analysis of the complex revealed an almost parallelogram geometry of the metal center, space group P with a = 12.3870(13), b = 12.9673(12), c = 14.3998(4) Å, α = 67.53(2), β = 75.34(2), γ = 86.89(3)°, V = 2065.5(3) Å3, Mr = 773.32, Z = 2, Dc = 1.243 g/cm3, μ = 0.489 mm-1, F(000) = 816, the final R = 0.0649 and wR = 0.1567. The compound was investigated for the catalytic behavior towards norbornene (NB) vinyl addition polymerization. And the complex exhibits high catalytic activities up to 1.668 × 107 g of PNB (mol of Pd)-1 h-1 with high monomer conversion using methylalumi-noxane (MAO) as the cocatalyst.
The title complex bis{1-[[(3-methyl-pyridin-2-yl) amino] methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol} palladium (C42H56O2N4Pd) has been synthesized by the reaction of 1-[[(3-methyl-pyridin-2-yl)amino]methyl-phenyl]-2-hydroxy-3,5-di-tert-butylphenol with Pd(OAc)2, and was characterized by IR and elemental analyses (C, H, N). Single-crystal X-ray diffraction analysis of the complex revealed an almost parallelogram geometry of the metal center, space group P with a = 12.3870(13), b = 12.9673(12), c = 14.3998(4) Å, α = 67.53(2), β = 75.34(2), γ = 86.89(3)°, V = 2065.5(3) Å3, Mr = 773.32, Z = 2, Dc = 1.243 g/cm3, μ = 0.489 mm-1, F(000) = 816, the final R = 0.0649 and wR = 0.1567. The compound was investigated for the catalytic behavior towards norbornene (NB) vinyl addition polymerization. And the complex exhibits high catalytic activities up to 1.668 × 107 g of PNB (mol of Pd)-1 h-1 with high monomer conversion using methylalumi-noxane (MAO) as the cocatalyst.
2016, 35(5): 796-804
doi: 10.14102/j.cnki.0254-5861.2011-0926
Abstract:
Two 1-methyl-1H-benzo[d]imidazole derivatives, C18H14CuN4O4·C4H8O2 (1) and C9H9N3O (2), have been synthesized and characterized by NMR, MS, FT-IR, elementary analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P21/n with a = 9.6888(3), b = 7.3772(2), c = 14.3277(4) Å, β = 95.819(3)°, V = 1018.81(5) Å3, Mr = 501.98, Z = 2, Dc = 1.636 g/cm3, F(000) = 518, μ = 1.123 mm-1, MoKα radiation (λ = 0.71073 Å), the final R = 0.0325 and wR = 0.0859 for 1821 observed reflections with I> 2σ(I). Compound 2 crystallizes in monoclinic, space group C2/c with a = 14.2908(14), b = 14.4268(13), c = 8.4802(6) Å, β = 108.513(9)°, V = 1657.9(3) Å3, Mr = 175.19, Z = 8, Dc = 1.404 g/cm3, F(000) = 736, μ = 0.097 mm-1, MoKα radiation (λ = 0.71073 Å), the final R = 0.0563 and wR = 0.1531 for 1231 observed reflections with I> 2σ(I). Intermolecular (N-H…N, N-H…O) and intramolecular (N-H…N, C-H…O) hydrogen bonds, as well as C-H…π and π-π stacking interactions, help to stabilize the crystal structure of compound 2.
Two 1-methyl-1H-benzo[d]imidazole derivatives, C18H14CuN4O4·C4H8O2 (1) and C9H9N3O (2), have been synthesized and characterized by NMR, MS, FT-IR, elementary analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P21/n with a = 9.6888(3), b = 7.3772(2), c = 14.3277(4) Å, β = 95.819(3)°, V = 1018.81(5) Å3, Mr = 501.98, Z = 2, Dc = 1.636 g/cm3, F(000) = 518, μ = 1.123 mm-1, MoKα radiation (λ = 0.71073 Å), the final R = 0.0325 and wR = 0.0859 for 1821 observed reflections with I> 2σ(I). Compound 2 crystallizes in monoclinic, space group C2/c with a = 14.2908(14), b = 14.4268(13), c = 8.4802(6) Å, β = 108.513(9)°, V = 1657.9(3) Å3, Mr = 175.19, Z = 8, Dc = 1.404 g/cm3, F(000) = 736, μ = 0.097 mm-1, MoKα radiation (λ = 0.71073 Å), the final R = 0.0563 and wR = 0.1531 for 1231 observed reflections with I> 2σ(I). Intermolecular (N-H…N, N-H…O) and intramolecular (N-H…N, C-H…O) hydrogen bonds, as well as C-H…π and π-π stacking interactions, help to stabilize the crystal structure of compound 2.
2016, 35(5): 805-810
doi: 10.14102/j.cnki.0254-5861.2011-0954
Abstract:
A new metal-organic network, [Cd(CH3OH)2(epa)]n (1), was synthesized from an achiral coupled cinnamic acid, 3,3'-((ethane-1,2-diylbis(oxy))bis(2,1-phenylene))diacrylic acid (H2epa), and Cd(NO3)2·4H2O under solvothermal conditions. The complex crystallizes in orthorhombic, space group P21212 with a = 9.8286(8), b = 21.0004(16), c = 5.5169(4) Å, V = 1138.71(15) Å3, Mr = 528.81, Dc = 1.542 Mg/cm3, F(000) = 536, Z = 2, the final R = 0.0345 and wR = 0.1101 for 2006 observed reflections (I> 2σ(I)). In 1 the epa2+ anions alternately bridge the Cd(II) cations to form a one-dimensional (1D) infinite homochiral helical chain of [Cd(epa)]n. The chiral homohelical chains via hydrogen bonds formed a two-dimensional (2D) network. The photoluminescence of 1 was also investigated in solid state at ambient temperature.
A new metal-organic network, [Cd(CH3OH)2(epa)]n (1), was synthesized from an achiral coupled cinnamic acid, 3,3'-((ethane-1,2-diylbis(oxy))bis(2,1-phenylene))diacrylic acid (H2epa), and Cd(NO3)2·4H2O under solvothermal conditions. The complex crystallizes in orthorhombic, space group P21212 with a = 9.8286(8), b = 21.0004(16), c = 5.5169(4) Å, V = 1138.71(15) Å3, Mr = 528.81, Dc = 1.542 Mg/cm3, F(000) = 536, Z = 2, the final R = 0.0345 and wR = 0.1101 for 2006 observed reflections (I> 2σ(I)). In 1 the epa2+ anions alternately bridge the Cd(II) cations to form a one-dimensional (1D) infinite homochiral helical chain of [Cd(epa)]n. The chiral homohelical chains via hydrogen bonds formed a two-dimensional (2D) network. The photoluminescence of 1 was also investigated in solid state at ambient temperature.
2016, 35(5): 811-817
doi: 10.14102/j.cnki.0254-5861.2011-0946
Abstract:
By using different anionic ancillary ligands, two new coordination polymers, [Cd(L)I2]n (1) and {[Cd(L)2(1,4-bdc)]·H2O}n (2) (L = 2,4,6-tris(4-pyridyl)pyridine, 1,4-H2bdc = benzene-1,4-dicarboxylic acid), have been synthesized under hydrothermal conditions. Compound 1 crystallizes in monoclinic, space group C2/c with a = 11.625(2), b = 13.871(3), c = 13.676(3) Å, β = 108.11(3)°, V = 2096.0(7) Å3, Dc = 2.144 g/cm3, C20H14I2N4Cd, Mr = 676.55, F(000) = 1264, µ(MoKα) = 3.999 mm–1, Z = 4, Rint = 0.0308, (Δρ)max = 0.354, (Δρ)min = 0.289, R = 0.0332 and wR = 0.0721 for 2401 observed reflections (I> 2s(I)). However, compound 2 crystallizes in triclinic, space group P with a = 10.315(2), b = 14.060(3), c = 15.090(3) Å, β = 98.40(3)°, V = 1990.0(9) Å3, Dc = 1.527 g/cm3, C48H34N8O5Cd, Mr = 915.23, F(000) = 932, µ(MoKα)= 0.610 mm–1, Z = 2, Rint = 0.0776, (Δρ)max = 0.869, (Δρ)min = 0.843, R = 0.0815 and wR = 0.1930 for 6999 observed reflections (I> 2s(I)). Compound 1 is a 1D chain structure, which adopts inorganic anion I- as the counterion, and 2 exists a 2D (4,4) network constructed by benzene-1,4-dicarboxylic acid.
By using different anionic ancillary ligands, two new coordination polymers, [Cd(L)I2]n (1) and {[Cd(L)2(1,4-bdc)]·H2O}n (2) (L = 2,4,6-tris(4-pyridyl)pyridine, 1,4-H2bdc = benzene-1,4-dicarboxylic acid), have been synthesized under hydrothermal conditions. Compound 1 crystallizes in monoclinic, space group C2/c with a = 11.625(2), b = 13.871(3), c = 13.676(3) Å, β = 108.11(3)°, V = 2096.0(7) Å3, Dc = 2.144 g/cm3, C20H14I2N4Cd, Mr = 676.55, F(000) = 1264, µ(MoKα) = 3.999 mm–1, Z = 4, Rint = 0.0308, (Δρ)max = 0.354, (Δρ)min = 0.289, R = 0.0332 and wR = 0.0721 for 2401 observed reflections (I> 2s(I)). However, compound 2 crystallizes in triclinic, space group P with a = 10.315(2), b = 14.060(3), c = 15.090(3) Å, β = 98.40(3)°, V = 1990.0(9) Å3, Dc = 1.527 g/cm3, C48H34N8O5Cd, Mr = 915.23, F(000) = 932, µ(MoKα)= 0.610 mm–1, Z = 2, Rint = 0.0776, (Δρ)max = 0.869, (Δρ)min = 0.843, R = 0.0815 and wR = 0.1930 for 6999 observed reflections (I> 2s(I)). Compound 1 is a 1D chain structure, which adopts inorganic anion I- as the counterion, and 2 exists a 2D (4,4) network constructed by benzene-1,4-dicarboxylic acid.
2016, 35(5): 818-826
doi: 10.14102/j.cnki.0254-5861.2011-0940
Abstract:
A novel tetrazylphosphonate ligand, namely ethyl 4-(2-ethyl-2H-1,2,3,4-tetrazol-5-yl) benzylphosphonate (Et-L), was designed and successfully achieved from p-cyano benzyl chloride, based on which a zinc coordination polymer (1) with a 2D layer structure has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TGA and X-ray single-crystal diffraction. The colorless block crystals of H2L·H2O were also obtained under the same hydrothermal conditions, which belongs to monoclinic system, space group P21/c with a = 13.3141(7), b = 5.1650(3), c = 21.9839(18) Å, β = 115.307(5)°, V = 1366.69(15) Å3, Z = 4, Dc = 1.391 mg/cm-3, Mr = 349.58, F(000) = 600, R = 0.0748 and wR = 0.1917 for 2392 observed reflections (I > 2σ(I)). The colorless block crystals of complex 1 ([Zn(L)(H2O)]n) also belong to monoclinic system, space group P21/c with a = 22.7464(10), b = 6.0430(3), c = 9.7704(4) Å, β = 92.525(4)°, V = 1341.70(10) Å3, Z = 4, Dc = 1.731 mg/cm-3, Mr = 349.58, F(000) = 712, R = 0.0596 and wR = 0.1688 for 2357 observed reflections (I > 2σ(I)). Only the oxygen atoms of phosphonic group are coordinated with the metal zinc probably because the hydrogen atom of tetrazole has been substituted by ethyl group. Photoluminescence properties of the complex are also investigated.
A novel tetrazylphosphonate ligand, namely ethyl 4-(2-ethyl-2H-1,2,3,4-tetrazol-5-yl) benzylphosphonate (Et-L), was designed and successfully achieved from p-cyano benzyl chloride, based on which a zinc coordination polymer (1) with a 2D layer structure has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TGA and X-ray single-crystal diffraction. The colorless block crystals of H2L·H2O were also obtained under the same hydrothermal conditions, which belongs to monoclinic system, space group P21/c with a = 13.3141(7), b = 5.1650(3), c = 21.9839(18) Å, β = 115.307(5)°, V = 1366.69(15) Å3, Z = 4, Dc = 1.391 mg/cm-3, Mr = 349.58, F(000) = 600, R = 0.0748 and wR = 0.1917 for 2392 observed reflections (I > 2σ(I)). The colorless block crystals of complex 1 ([Zn(L)(H2O)]n) also belong to monoclinic system, space group P21/c with a = 22.7464(10), b = 6.0430(3), c = 9.7704(4) Å, β = 92.525(4)°, V = 1341.70(10) Å3, Z = 4, Dc = 1.731 mg/cm-3, Mr = 349.58, F(000) = 712, R = 0.0596 and wR = 0.1688 for 2357 observed reflections (I > 2σ(I)). Only the oxygen atoms of phosphonic group are coordinated with the metal zinc probably because the hydrogen atom of tetrazole has been substituted by ethyl group. Photoluminescence properties of the complex are also investigated.
