The optimized geometric structure and photophysical properties of 6-Amino-2-methylpyridine-3-carbonitrile dye have been studied by using Density Functional Theory (DFT). The lowest singlet excited state geometry optim...The optimized geometric structure and photophysical properties of 6-Amino-2-methylpyridine-3-carbonitrile dye have been studied by using Density Functional Theory (DFT). The lowest singlet excited state geometry optimized using Time-Dependent Density Functional Theory (TD-DFT). On the basis of ground and excited state geometries, the absorption spectra have been calculated using the DFT and TD-DFT method in gas phase and acetonitrile medium. To understand the Non-Linear Optical properties of 6-Amino-2-methylpyridine-3-carbonitrile dye, we computed dipole moment (μ), electronic polarizability (α), and first hyperpolarizability (β0) and second order hyperpolarizability (γ) using B3LYP density functional theory method in conjunction with 6-311++G(d) basis set.展开更多
A new complex[Co（NIPH）（mbix）]n（1,H2NIPH = 5-nitroisophthalic acid,mbix =l,3-bis（imidazol-l-ylmethyl）benzene） has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum...A new complex[Co（NIPH）（mbix）]n（1,H2NIPH = 5-nitroisophthalic acid,mbix =l,3-bis（imidazol-l-ylmethyl）benzene） has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,UV spectrum,TG and single-crystal X-ray diffraction.Pink crystals crystallize in the triclinic system,space group P1 with a = 8.3797（8）,b= 10.2522（10）,c= 13.4244（13） A,α=94.820（2）,β=108.105（2）,γ=104.816（2）°,V=1042.84（17） A^3,C（22）H（17）CoN5O6,Mr = 506.34,Dc = 1.613 g/cm^3,F（000） = 518,Z = 2,μ（MoKα） =0.876 mm^（-1）,the final R = 0.0505 and wR = 0.1254 for 3267 observed reflections（I〉2σ（I））.The structure of 1 exhibits a two-dimensional network structure and is extended into a three-dimensional supramolecule through hydrogen bonds and n-n interactions.In addition,Natural Bond Orbital（NBO） analysis was performed by using the PBE0/LANL2 DZ method built in Gaussian 09 Program.The calculation results showed obvious covalent interactions between the coordinated atoms and Co（Ⅱ） ion.展开更多
运用量子化学从头算方法,在MP2/6-311++G(d,p),MP2/6-311++G(2df,2p),MP2/6-311++G(3df,3pd)和QCISD/6-311++G(d,p)水平上,研究了CH3F,CH3Cl和CH3Br作为质子给体与Cl-,Br-作为质子接受体形成的氢键CH3…Y.计算结果表明:6种复合物中C—H...运用量子化学从头算方法,在MP2/6-311++G(d,p),MP2/6-311++G(2df,2p),MP2/6-311++G(3df,3pd)和QCISD/6-311++G(d,p)水平上,研究了CH3F,CH3Cl和CH3Br作为质子给体与Cl-,Br-作为质子接受体形成的氢键CH3…Y.计算结果表明:6种复合物中C—H键收缩,伸缩振动频率增大,形成蓝移氢键.分子中原子(AtomsinMole-cules,AIM)分析表明,这些复合物的电子密度拓扑性质与普通氢键有着本质的不同,在Y…H之间不存在键临界点,而在Y与C之间存在键临界点,因此这些相互作用严格地不能称为氢键.自然键轨道(Natural bond orbital,NBO)分析表明,在这些复合物中弯曲的CH…Y的特殊结构使得分子间超共轭n(Y)→σ*(C—H)减小到可以忽略;质子接受体的电子密度没有转移到σ*(C—H)上,而是转移到了σ*(C—X)(X=F,Cl,Br)上;存在一定程度的重杂化;分子内超共轭相互作用减小使得σ*(C—H)的电子密度减少.这些因素共同导致C—H伸缩振动频率的蓝移.展开更多
A new metal-organic coordination polymer [Ni（oba）（mbix）（H2O）]n·n H2O（H2oba = 4,4‘-oxydibenzoic acid,mbix = 1,3-bis（imidazol-1-ylmethyl）-benzene） 1 has been hydrothermally synthesized and structurally c...A new metal-organic coordination polymer [Ni（oba）（mbix）（H2O）]n·n H2O（H2oba = 4,4‘-oxydibenzoic acid,mbix = 1,3-bis（imidazol-1-ylmethyl）-benzene） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR,TG,UV and single-crystal X-ray diffraction.Green crystals crystallize in the triclinic system,space group P1 with a = 10.1915（18）,b = 11.415（2）,c = 12.314（2）A,α = 74.263（3）,β = 84.545（2）,γ = 74.369（3）o,V = 1327.6（4） A,C28H26N4 Ni O7,Mr = 589.24,Dc = 1.474 g/cm3,F（000） = 612,Z = 2,μ（Mo Kα） = 0.786 mm-1,the final R = 0.0332 and w R = 0.0869 for 4622 observed reflections（I 〉 2σ（I））.The structure of 1 exhibits a one-dimensional chain-like structure.In addition,natural bond orbital（NBO） analysis was performed by the PBE0/LANL2 DZ method in Gaussian 03 Program.The calculation results show obvious covalent interaction between the coordinated atoms and Ni（Ⅱ） ion.展开更多
A new 2D coordination polymer, {[Cd5(BTC)2(L)4(H2O)2]n·2H2O}n(1, H3BTC = 1,3,5-benzenetricarboxylic acid, HL = 3-(2-pyridyl)pyrazole) was synthesized under hydrothermal conditions and characterized by single-crys...A new 2D coordination polymer, {[Cd5(BTC)2(L)4(H2O)2]n·2H2O}n(1, H3BTC = 1,3,5-benzenetricarboxylic acid, HL = 3-(2-pyridyl)pyrazole) was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, IR, TGA, fluorescence spectrum and elemental analysis techniques. Complex 1 belongs to the monoclinic system, P21/c space group, with a = 8.8732(4), b = 17.5179(7), c = 17.8123(7) ?, β = 103.1830(10)°, V = 2695.77(19) ?3 and Z = 2. It features a 2D network constructed by BTC and L ligand. In addition, we analyzed Natural Bond Orbital(NBO) by using the PBE0/LANL2DZ method built in Gaussian 09 Program. The calculation results indicated obvious covalent interactions between the coordinated atoms and Cd(Ⅱ) ion.展开更多
A new coordination polymer, [Cd2（NIPH）（L）2（H2O）]n（1, HL = 3-（2-pyridyl）pyrazole and H2NIPH = 5-nitroisophthalic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-...A new coordination polymer, [Cd2（NIPH）（L）2（H2O）]n（1, HL = 3-（2-pyridyl）pyrazole and H2NIPH = 5-nitroisophthalic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis, thermogravimetric analysis and fluorescence spectrum analysis. Complex 1 belongs to the triclinic system, space group P1 with a = 8.9539（6）, b = 11.6252（8）, c = 12.2472（8） A^°, α = 80.011（2）, β = 80.3850（10）, γ = 86.773（2）°, V = 1237.37（14） A^°3, Z = 2, Dc = 1.987 g/cm^3, μ = 1.780 mm^-1, Mr = 740.25, F（000） = 724, the final R = 0.0295 and wR = 0.1015 with I 〉 2σ（I）. Two H2NIPH as monodentate and bidentate ligands and two L ligands link four Cd（Ⅱ） ions to form a tetranuclear subunit. Each pair of the tetranuclear subunits is bridged by NIPH ligands to yield a one-dimensional double-chain structure. Furthermore, the 1D chains are linked into a 3D supramolecular framework with hydrogen bonds and π-π interactions. In addition, we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2DZ method built in Gaussian 03 Program. The calculation results indicated the obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.展开更多
文摘The optimized geometric structure and photophysical properties of 6-Amino-2-methylpyridine-3-carbonitrile dye have been studied by using Density Functional Theory (DFT). The lowest singlet excited state geometry optimized using Time-Dependent Density Functional Theory (TD-DFT). On the basis of ground and excited state geometries, the absorption spectra have been calculated using the DFT and TD-DFT method in gas phase and acetonitrile medium. To understand the Non-Linear Optical properties of 6-Amino-2-methylpyridine-3-carbonitrile dye, we computed dipole moment (μ), electronic polarizability (α), and first hyperpolarizability (β0) and second order hyperpolarizability (γ) using B3LYP density functional theory method in conjunction with 6-311++G(d) basis set.
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 complex[Co（NIPH）（mbix）]n（1,H2NIPH = 5-nitroisophthalic acid,mbix =l,3-bis（imidazol-l-ylmethyl）benzene） has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,UV spectrum,TG and single-crystal X-ray diffraction.Pink crystals crystallize in the triclinic system,space group P1 with a = 8.3797（8）,b= 10.2522（10）,c= 13.4244（13） A,α=94.820（2）,β=108.105（2）,γ=104.816（2）°,V=1042.84（17） A^3,C（22）H（17）CoN5O6,Mr = 506.34,Dc = 1.613 g/cm^3,F（000） = 518,Z = 2,μ（MoKα） =0.876 mm^（-1）,the final R = 0.0505 and wR = 0.1254 for 3267 observed reflections（I〉2σ（I））.The structure of 1 exhibits a two-dimensional network structure and is extended into a three-dimensional supramolecule through hydrogen bonds and n-n interactions.In addition,Natural Bond Orbital（NBO） analysis was performed by using the PBE0/LANL2 DZ method built in Gaussian 09 Program.The calculation results showed obvious covalent interactions between the coordinated atoms and Co（Ⅱ） ion.
文摘运用量子化学从头算方法,在MP2/6-311++G(d,p),MP2/6-311++G(2df,2p),MP2/6-311++G(3df,3pd)和QCISD/6-311++G(d,p)水平上,研究了CH3F,CH3Cl和CH3Br作为质子给体与Cl-,Br-作为质子接受体形成的氢键CH3…Y.计算结果表明:6种复合物中C—H键收缩,伸缩振动频率增大,形成蓝移氢键.分子中原子(AtomsinMole-cules,AIM)分析表明,这些复合物的电子密度拓扑性质与普通氢键有着本质的不同,在Y…H之间不存在键临界点,而在Y与C之间存在键临界点,因此这些相互作用严格地不能称为氢键.自然键轨道(Natural bond orbital,NBO)分析表明,在这些复合物中弯曲的CH…Y的特殊结构使得分子间超共轭n(Y)→σ*(C—H)减小到可以忽略;质子接受体的电子密度没有转移到σ*(C—H)上,而是转移到了σ*(C—X)(X=F,Cl,Br)上;存在一定程度的重杂化;分子内超共轭相互作用减小使得σ*(C—H)的电子密度减少.这些因素共同导致C—H伸缩振动频率的蓝移.
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 metal-organic coordination polymer [Ni（oba）（mbix）（H2O）]n·n H2O（H2oba = 4,4‘-oxydibenzoic acid,mbix = 1,3-bis（imidazol-1-ylmethyl）-benzene） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR,TG,UV and single-crystal X-ray diffraction.Green crystals crystallize in the triclinic system,space group P1 with a = 10.1915（18）,b = 11.415（2）,c = 12.314（2）A,α = 74.263（3）,β = 84.545（2）,γ = 74.369（3）o,V = 1327.6（4） A,C28H26N4 Ni O7,Mr = 589.24,Dc = 1.474 g/cm3,F（000） = 612,Z = 2,μ（Mo Kα） = 0.786 mm-1,the final R = 0.0332 and w R = 0.0869 for 4622 observed reflections（I 〉 2σ（I））.The structure of 1 exhibits a one-dimensional chain-like structure.In addition,natural bond orbital（NBO） analysis was performed by the PBE0/LANL2 DZ method in Gaussian 03 Program.The calculation results show obvious covalent interaction between the coordinated atoms and Ni（Ⅱ） ion.
基金supported by the Science and Technology development plan of Jilin Province(2015052006JH)
文摘A new 2D coordination polymer, {[Cd5(BTC)2(L)4(H2O)2]n·2H2O}n(1, H3BTC = 1,3,5-benzenetricarboxylic acid, HL = 3-(2-pyridyl)pyrazole) was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, powder XRD, IR, TGA, fluorescence spectrum and elemental analysis techniques. Complex 1 belongs to the monoclinic system, P21/c space group, with a = 8.8732(4), b = 17.5179(7), c = 17.8123(7) ?, β = 103.1830(10)°, V = 2695.77(19) ?3 and Z = 2. It features a 2D network constructed by BTC and L ligand. In addition, we analyzed Natural Bond Orbital(NBO) by using the PBE0/LANL2DZ method built in Gaussian 09 Program. The calculation results indicated obvious covalent interactions between the coordinated atoms and Cd(Ⅱ) ion.
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 coordination polymer, [Cd2（NIPH）（L）2（H2O）]n（1, HL = 3-（2-pyridyl）pyrazole and H2NIPH = 5-nitroisophthalic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis, thermogravimetric analysis and fluorescence spectrum analysis. Complex 1 belongs to the triclinic system, space group P1 with a = 8.9539（6）, b = 11.6252（8）, c = 12.2472（8） A^°, α = 80.011（2）, β = 80.3850（10）, γ = 86.773（2）°, V = 1237.37（14） A^°3, Z = 2, Dc = 1.987 g/cm^3, μ = 1.780 mm^-1, Mr = 740.25, F（000） = 724, the final R = 0.0295 and wR = 0.1015 with I 〉 2σ（I）. Two H2NIPH as monodentate and bidentate ligands and two L ligands link four Cd（Ⅱ） ions to form a tetranuclear subunit. Each pair of the tetranuclear subunits is bridged by NIPH ligands to yield a one-dimensional double-chain structure. Furthermore, the 1D chains are linked into a 3D supramolecular framework with hydrogen bonds and π-π interactions. In addition, we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2DZ method built in Gaussian 03 Program. The calculation results indicated the obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.
