In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properti...In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properties of the complexes. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods have been used. The ground state geometries, binding energies, spectral properties (UV-vis), frontier molecular orbitals (FMOs) analysis, charge analysis and natural bond orbital (NBO) have been investigated. The geometrical parameters are in good agreement with the available experimental data. The metal-ligand binding energies are 1 order of magnitude larger than the physisorption energy of a benzene-1, 2-dthiolate molecule on a metallic surface. The electronic structures of the first raw transition metal series from V to Co have been elucidated by UV-vis spectroscopic using DFT calculations. In accordance with experiment the calculated electronic spectra of these tris complexes show bands at 522, 565, 559, 546 and 863 nm for V3+, Cr3+, Mn3+, Fe3+ and Co3+ respectively which are mainly attributed to ligand to metal charge transfer (LMCT) transitions. The electronic properties analysis shows that the highest occupied molecular orbital (HOMO) is mainly centered on metal coordinated sulfur atoms whereas the lowest unoccupied molecular orbital (LUMO) is mainly located on the metal surface. From calculation of intramolecular interactions and electron delocalization by natural bond orbital (NBO) analysis, the stability of the complexes was estimated. The NBO results showed significant charge transfer from sulfur to central metal ions in the complexes, as well as to the benzene. The calculated charges on metal ions are also reported at various charge schemes. The calculations show encouraging agreement with the available experimental data.展开更多
A novel coordination polymer, [Co3（bta）2（dpe）3（H2O）2]·2H2O （1, H3bta = benzene-1,3,5-triacetic acid, and dpe = 1,2-di（pyridin-4-yl）ethene）, has been hydrothermally prepared and characterized by IR spect...A novel coordination polymer, [Co3（bta）2（dpe）3（H2O）2]·2H2O （1, H3bta = benzene-1,3,5-triacetic acid, and dpe = 1,2-di（pyridin-4-yl）ethene）, has been hydrothermally prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal is of triclinic system, space group P , with a = 9.5687（15）, b = 11.2470（17）, c = 13.686（2） , α = 78.262（3）, β = 89.271（4）, γ = 81.292（3）°, V = 1425.2（4） 3, C60H56N6O16Co3, Mr = 1293.90, Dc = 1.508 g/cm3, F（000） = 667, μ = 0.940 mm-1 and Z = 1. The final R = 0.0707 and wR = 0.1413 for 4950 observed reflections （I 2σ（I））. In the title complex, the bta ligand acts as a four-dentate bridging ligand to link up cobalt atoms into lamellar frameworks which are further interlinked by the dpe ligands to generate a trinodal （3,4,6）-connected （4.62）2（42.68.83.102）（64.82） net.展开更多
The optical properties of N,N’-bis (Inaphthyl)N,N’-diphenyl-1,1’-biphenyl-4,4’-diamine (NPB) and tris (8-hydroxyquinolinato) aluminum (Alq3) organic materials used as hole transport and electron transport layers i...The optical properties of N,N’-bis (Inaphthyl)N,N’-diphenyl-1,1’-biphenyl-4,4’-diamine (NPB) and tris (8-hydroxyquinolinato) aluminum (Alq3) organic materials used as hole transport and electron transport layers in organic light-emitting devices (OLED) have been investigated. The NPB and Alq3 layers were prepared using thermal evaporation method. The results show that the energy band gap of Alq3 is thickness independence while the energy band gap of NPB decreases with the increasing of sample thickness. For the case of photoluminescence the Alq3 with thickness of 84 nm shows the highest relative intensity peak at 510 nm.展开更多
A rare earth Schiff base complex:lanthanum tris(N-phenylethyl-3,5-di-t-butylsalicylaldiminato)s [La(OPEBS)_3] was successfully applied as single component initiator for the ring-opening polymerization of 1,4-dioxan-2-...A rare earth Schiff base complex:lanthanum tris(N-phenylethyl-3,5-di-t-butylsalicylaldiminato)s [La(OPEBS)_3] was successfully applied as single component initiator for the ring-opening polymerization of 1,4-dioxan-2-one (PDO) in bulk.The influence of reaction conditions,such as polymerization temperature,the molar ratio of the monomer to initiator (M/I) on the monomer conversion and molecular weight of the polymer has been investigated.Poly(1,4-dioxan-2-one) with a viscosity-average molecular weight (My) o...展开更多
The title complex,[（BBI）Mn（BDC）]n 1（BBI = 2,2＇-bisbenzimidazole（C14H10N4）,BDC=benzene-1,3-dicarboxylate dianion（C8H10O4））,crystallizes in the monoclinic system,space group C2/c,with a=17.822（8）,b=16.181（...The title complex,[（BBI）Mn（BDC）]n 1（BBI = 2,2＇-bisbenzimidazole（C14H10N4）,BDC=benzene-1,3-dicarboxylate dianion（C8H10O4））,crystallizes in the monoclinic system,space group C2/c,with a=17.822（8）,b=16.181（7）,c=13.355（6）A,β=92.112（5）°,V=3848.67（304）A^3,Z=8,C22H14MnN4O4,Mr=453.31,Dc=1.565 g/cm^3,F（000）=1848,μ=0.725 mm^-1,S=1.000,the final R=0.0310 and wR=0.0589.1 contains hydrogen bonds and π-π stacking interactions between the neighboring aryl-ring of BBI＇s,which helps to form a three-dimensional crystal structure.展开更多
A range of new compounds such as N1,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6HsN（Ar）z}ZrCl4] （Ar = C6H5） complex counting the chelating amine and chloride in position tra...A range of new compounds such as N1,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6HsN（Ar）z}ZrCl4] （Ar = C6H5） complex counting the chelating amine and chloride in position trans have been prepared. Well-defined NI,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6H5N（Ar）2}ZrCl4] （Ar = C6H5） was obtained by stoichiometric addition of {（Ar）2NC6H5N（Ar）2} （Ar = C6H5） and {ZrC14} in ethanol at reflex temperature. IR, 1H NMR, electronic properties using hyperchem program study has been improved for this compound such as bond distance, and this compound was also defined as electric conductivity which proves to be useful for conductively compound.展开更多
将三(1-氧代-1-磷杂-2,6,7-三氧杂双环[2,2,2]辛烷-4-亚甲基)磷酸酯(trimer)用于阻燃聚碳酸酯(PC),研究了它对 PC 阻燃性能、机械性能、热分解行为及灼烧残炭的影响。将 trimer 用于 PC 时,其质量分数为8%的用量即可使 PC 的阻燃级别达...将三(1-氧代-1-磷杂-2,6,7-三氧杂双环[2,2,2]辛烷-4-亚甲基)磷酸酯(trimer)用于阻燃聚碳酸酯(PC),研究了它对 PC 阻燃性能、机械性能、热分解行为及灼烧残炭的影响。将 trimer 用于 PC 时,其质量分数为8%的用量即可使 PC 的阻燃级别达到 UL 94 V-O(试样厚度为3.2 mm)级,极限氧指数达33%。值得注意的是,加入 trimer 可改善 PC 的拉伸强度,特别是弯曲强度及弯曲模量。热分析数据表明,trimer 可提前并加速 PC 的交联成炭,但不能提高PC 的成炭率。此外,扫描电子最微镜照片显示,trimer 可使炭层轻微发泡膨胀,也可改善炭层质量。展开更多
A tripod ligand, 1,1,1 tri [1′ (2′ oxa 5′ oxo 6′ aza 6′ bisphenyl)hexyl] propane(L), and its complexes with Ln(NO 3) 3 · n H 2O(where Ln=La, Ce, Pr, Nd) have been synthesized. These new complexes with the ge...A tripod ligand, 1,1,1 tri [1′ (2′ oxa 5′ oxo 6′ aza 6′ bisphenyl)hexyl] propane(L), and its complexes with Ln(NO 3) 3 · n H 2O(where Ln=La, Ce, Pr, Nd) have been synthesized. These new complexes with the general formula of Ln 2L(NO 3) 6· n H 2O(where Ln=La, n =4; Ln=Pr, n =2; Ln=Ce, Nd, n =1) were characterized by elemental analysis, IR spectra, thermal analysis, 1H NMR spectra and molar conductivity. All the complexes are stable in air and their conductances in acetonitrile solution lie in the 149—158 S·cm 2·mol -1 range, indicating that they are 1∶1 type electrolytes. The IR and 1H NMR spectra of the ligand and its complexes show that all the ether oxygen atoms and the CO groups take part in coordination to the metal ions, and the larger shift for ν CO in the IR spectra of the complexes suggests that the Ln—O(carbonyl) bond is stronger than the Ln—O(ether) one which also was inferred from the 1H NMR spectral data . The thermal behaviour of the complexes are similar. The first loss occurs at 85—100.9 ℃ corresponding to the loss of all the water molecules. The weight losses found in this process compare favourably with the theoretical values. Moreover, the relatively low temperatures of dehydration are consistent with the presence of crystal water.展开更多
文摘In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properties of the complexes. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods have been used. The ground state geometries, binding energies, spectral properties (UV-vis), frontier molecular orbitals (FMOs) analysis, charge analysis and natural bond orbital (NBO) have been investigated. The geometrical parameters are in good agreement with the available experimental data. The metal-ligand binding energies are 1 order of magnitude larger than the physisorption energy of a benzene-1, 2-dthiolate molecule on a metallic surface. The electronic structures of the first raw transition metal series from V to Co have been elucidated by UV-vis spectroscopic using DFT calculations. In accordance with experiment the calculated electronic spectra of these tris complexes show bands at 522, 565, 559, 546 and 863 nm for V3+, Cr3+, Mn3+, Fe3+ and Co3+ respectively which are mainly attributed to ligand to metal charge transfer (LMCT) transitions. The electronic properties analysis shows that the highest occupied molecular orbital (HOMO) is mainly centered on metal coordinated sulfur atoms whereas the lowest unoccupied molecular orbital (LUMO) is mainly located on the metal surface. From calculation of intramolecular interactions and electron delocalization by natural bond orbital (NBO) analysis, the stability of the complexes was estimated. The NBO results showed significant charge transfer from sulfur to central metal ions in the complexes, as well as to the benzene. The calculated charges on metal ions are also reported at various charge schemes. The calculations show encouraging agreement with the available experimental data.
基金supported by the National Natural Science Foundation of China (No. 20971004)the Natural Science Foundation of Anhui Province (No. 11040606M45)
文摘A novel coordination polymer, [Co3（bta）2（dpe）3（H2O）2]·2H2O （1, H3bta = benzene-1,3,5-triacetic acid, and dpe = 1,2-di（pyridin-4-yl）ethene）, has been hydrothermally prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal is of triclinic system, space group P , with a = 9.5687（15）, b = 11.2470（17）, c = 13.686（2） , α = 78.262（3）, β = 89.271（4）, γ = 81.292（3）°, V = 1425.2（4） 3, C60H56N6O16Co3, Mr = 1293.90, Dc = 1.508 g/cm3, F（000） = 667, μ = 0.940 mm-1 and Z = 1. The final R = 0.0707 and wR = 0.1413 for 4950 observed reflections （I 2σ（I））. In the title complex, the bta ligand acts as a four-dentate bridging ligand to link up cobalt atoms into lamellar frameworks which are further interlinked by the dpe ligands to generate a trinodal （3,4,6）-connected （4.62）2（42.68.83.102）（64.82） net.
文摘The optical properties of N,N’-bis (Inaphthyl)N,N’-diphenyl-1,1’-biphenyl-4,4’-diamine (NPB) and tris (8-hydroxyquinolinato) aluminum (Alq3) organic materials used as hole transport and electron transport layers in organic light-emitting devices (OLED) have been investigated. The NPB and Alq3 layers were prepared using thermal evaporation method. The results show that the energy band gap of Alq3 is thickness independence while the energy band gap of NPB decreases with the increasing of sample thickness. For the case of photoluminescence the Alq3 with thickness of 84 nm shows the highest relative intensity peak at 510 nm.
基金supported by the National Natural Science Foundation of China (Key program,Nos.G20434020 and G20774078).
文摘A rare earth Schiff base complex:lanthanum tris(N-phenylethyl-3,5-di-t-butylsalicylaldiminato)s [La(OPEBS)_3] was successfully applied as single component initiator for the ring-opening polymerization of 1,4-dioxan-2-one (PDO) in bulk.The influence of reaction conditions,such as polymerization temperature,the molar ratio of the monomer to initiator (M/I) on the monomer conversion and molecular weight of the polymer has been investigated.Poly(1,4-dioxan-2-one) with a viscosity-average molecular weight (My) o...
文摘The title complex,[（BBI）Mn（BDC）]n 1（BBI = 2,2＇-bisbenzimidazole（C14H10N4）,BDC=benzene-1,3-dicarboxylate dianion（C8H10O4））,crystallizes in the monoclinic system,space group C2/c,with a=17.822（8）,b=16.181（7）,c=13.355（6）A,β=92.112（5）°,V=3848.67（304）A^3,Z=8,C22H14MnN4O4,Mr=453.31,Dc=1.565 g/cm^3,F（000）=1848,μ=0.725 mm^-1,S=1.000,the final R=0.0310 and wR=0.0589.1 contains hydrogen bonds and π-π stacking interactions between the neighboring aryl-ring of BBI＇s,which helps to form a three-dimensional crystal structure.
文摘A range of new compounds such as N1,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6HsN（Ar）z}ZrCl4] （Ar = C6H5） complex counting the chelating amine and chloride in position trans have been prepared. Well-defined NI,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6H5N（Ar）2}ZrCl4] （Ar = C6H5） was obtained by stoichiometric addition of {（Ar）2NC6H5N（Ar）2} （Ar = C6H5） and {ZrC14} in ethanol at reflex temperature. IR, 1H NMR, electronic properties using hyperchem program study has been improved for this compound such as bond distance, and this compound was also defined as electric conductivity which proves to be useful for conductively compound.
文摘将三(1-氧代-1-磷杂-2,6,7-三氧杂双环[2,2,2]辛烷-4-亚甲基)磷酸酯(trimer)用于阻燃聚碳酸酯(PC),研究了它对 PC 阻燃性能、机械性能、热分解行为及灼烧残炭的影响。将 trimer 用于 PC 时,其质量分数为8%的用量即可使 PC 的阻燃级别达到 UL 94 V-O(试样厚度为3.2 mm)级,极限氧指数达33%。值得注意的是,加入 trimer 可改善 PC 的拉伸强度,特别是弯曲强度及弯曲模量。热分析数据表明,trimer 可提前并加速 PC 的交联成炭,但不能提高PC 的成炭率。此外,扫描电子最微镜照片显示,trimer 可使炭层轻微发泡膨胀,也可改善炭层质量。
文摘A tripod ligand, 1,1,1 tri [1′ (2′ oxa 5′ oxo 6′ aza 6′ bisphenyl)hexyl] propane(L), and its complexes with Ln(NO 3) 3 · n H 2O(where Ln=La, Ce, Pr, Nd) have been synthesized. These new complexes with the general formula of Ln 2L(NO 3) 6· n H 2O(where Ln=La, n =4; Ln=Pr, n =2; Ln=Ce, Nd, n =1) were characterized by elemental analysis, IR spectra, thermal analysis, 1H NMR spectra and molar conductivity. All the complexes are stable in air and their conductances in acetonitrile solution lie in the 149—158 S·cm 2·mol -1 range, indicating that they are 1∶1 type electrolytes. The IR and 1H NMR spectra of the ligand and its complexes show that all the ether oxygen atoms and the CO groups take part in coordination to the metal ions, and the larger shift for ν CO in the IR spectra of the complexes suggests that the Ln—O(carbonyl) bond is stronger than the Ln—O(ether) one which also was inferred from the 1H NMR spectral data . The thermal behaviour of the complexes are similar. The first loss occurs at 85—100.9 ℃ corresponding to the loss of all the water molecules. The weight losses found in this process compare favourably with the theoretical values. Moreover, the relatively low temperatures of dehydration are consistent with the presence of crystal water.
