The coordination structure of cupric tartrate(Cu−TA)complex was investigated by ultraviolet−visible(UV-Vis)and liquid chromatography/mass spectrometer(LC-MS)firstly;furthermore,effective coordination configurations an...The coordination structure of cupric tartrate(Cu−TA)complex was investigated by ultraviolet−visible(UV-Vis)and liquid chromatography/mass spectrometer(LC-MS)firstly;furthermore,effective coordination configurations and electronic properties of Cu−TA in aqueous solution were systematically revealed by density functional theory(DFT)calculations.Consistently,Job plots show the possible existence of[Cu(TA)]and[Cu(TA)_(2)]^(2-)at 230 and 255 nm based on UV-Vis results.LC-MS results confirm the existence of the single and high coordination complexes[Cu_(2)(TA)_(2)]^(+),[Cu(TA)_(2)]^(+)and[Cu_(2)(TA)_(3)(H_(2)O)_(2)(OH)_(2)]^(2+).DFT calculation results show that carboxylic oxygen and hydroxyl oxygen of tartaric acid(TA)are preferred sites for Cu(Ⅱ)coordination.[Cu(TA)](1H,3H sites O of TA coordinated with Cu(Ⅱ)),[Cu(TA)_(2)]^(2-)(two 1^(C),2^(H) sites O of TA coordinated with Cu(Ⅱ)),and[Cu(TA)_(3)]^(4-)(three 2H,3H sites O of TA coordinated with Cu(Ⅱ))should be dominant coordination configurations of Cu−TA.The corresponding Gibbs reaction energies are-170.1,-136.2,and-90.2 kJ/mol,respectively.展开更多
Two cupric complexes containing methylbenzoic acid have been prepared and crystallized by solvent evaporation method in DMF. The single-crystal X-ray crystallographic analysis reveals that they are dicaryon complexes....Two cupric complexes containing methylbenzoic acid have been prepared and crystallized by solvent evaporation method in DMF. The single-crystal X-ray crystallographic analysis reveals that they are dicaryon complexes. Complex I with formula of [Cu2（m- MBA）4DMF2] crystallizes in monoclinic with space group of P21/c and complex 2 with formula of [Cuz（o-MBA）ffo-phen）2]·NO3·H2O crystallizes in triclinic with space group of P I. The weak interactions including C-H...O hydrogen bonds, C-H…π interactions and π-π stacking in the structures of two complexes are observed from the X-ray crystallographic data. In addition, there are still classical hydrogen bonds in 2. The different strength of intermolecular interaction in the structure is reflected on their different thermal stability measured by thermal gravimetric analysis and 2D-1R correlation spectroscopy of two complexes. The study of weak interactions is meaningful to provide supporting data for supramolecular chemistry theory and potential applications in molecular biology.展开更多
The reaction ofphenyl 2-pyridyl ketoxime （PhPyCNOH） with Cu（NO3）2·3H2O has led to a triangular complex Cu3（OH）（PhPyCNO）3（NO3）·NO3·H2O 1 containing the [Cu3（μ2-OH）]5＋ core and possessing th...The reaction ofphenyl 2-pyridyl ketoxime （PhPyCNOH） with Cu（NO3）2·3H2O has led to a triangular complex Cu3（OH）（PhPyCNO）3（NO3）·NO3·H2O 1 containing the [Cu3（μ2-OH）]5＋ core and possessing the very rare inverse 9-metallacrown-3 motif created by the bridging oximate groups. Crystallographic data for 1： C36H30N8O11CU3, Mr = 941.30, monoclinic, space group C2/c, a = 18.815（9）, b = 33.888（15）, c = 14.307（7） A, β = 118.945（6）°, V= 7983（6） A3, Z = 8, Dc = 1.566 g/cm3, μ = 1.652 mm^-1, F（000） = 3816, R= 0.0644 and wR= 0.1393 for 3468 observed reflections （I〉 2σ（I））. Preliminary variable-temperature magnetic susceptibility studies reveal an antiferromagnetically-coupled system showing antisymmetrie exchange.展开更多
基金the National Key Research and Development Program of China(No.2019YFC0408303)the Natural Science Foundation of Hunan Province,China(No.2021JJ20069)+2 种基金the Changsha Science and Technology Project,China(Nos.kq2106016,kq2009005)Higher Education Discipline Innovation Project(111 Project),China(No.B14034)the Fundamental Research Funds for the Central Universities of Central South University,China(No.2021zzts0887).
文摘The coordination structure of cupric tartrate(Cu−TA)complex was investigated by ultraviolet−visible(UV-Vis)and liquid chromatography/mass spectrometer(LC-MS)firstly;furthermore,effective coordination configurations and electronic properties of Cu−TA in aqueous solution were systematically revealed by density functional theory(DFT)calculations.Consistently,Job plots show the possible existence of[Cu(TA)]and[Cu(TA)_(2)]^(2-)at 230 and 255 nm based on UV-Vis results.LC-MS results confirm the existence of the single and high coordination complexes[Cu_(2)(TA)_(2)]^(+),[Cu(TA)_(2)]^(+)and[Cu_(2)(TA)_(3)(H_(2)O)_(2)(OH)_(2)]^(2+).DFT calculation results show that carboxylic oxygen and hydroxyl oxygen of tartaric acid(TA)are preferred sites for Cu(Ⅱ)coordination.[Cu(TA)](1H,3H sites O of TA coordinated with Cu(Ⅱ)),[Cu(TA)_(2)]^(2-)(two 1^(C),2^(H) sites O of TA coordinated with Cu(Ⅱ)),and[Cu(TA)_(3)]^(4-)(three 2H,3H sites O of TA coordinated with Cu(Ⅱ))should be dominant coordination configurations of Cu−TA.The corresponding Gibbs reaction energies are-170.1,-136.2,and-90.2 kJ/mol,respectively.
基金Science and Technology Project of Education Department of Fujian Province(JA11286)Science and Technology Development Fund of Fuzhou University(2010-XQ-09)
文摘Two cupric complexes containing methylbenzoic acid have been prepared and crystallized by solvent evaporation method in DMF. The single-crystal X-ray crystallographic analysis reveals that they are dicaryon complexes. Complex I with formula of [Cu2（m- MBA）4DMF2] crystallizes in monoclinic with space group of P21/c and complex 2 with formula of [Cuz（o-MBA）ffo-phen）2]·NO3·H2O crystallizes in triclinic with space group of P I. The weak interactions including C-H...O hydrogen bonds, C-H…π interactions and π-π stacking in the structures of two complexes are observed from the X-ray crystallographic data. In addition, there are still classical hydrogen bonds in 2. The different strength of intermolecular interaction in the structure is reflected on their different thermal stability measured by thermal gravimetric analysis and 2D-1R correlation spectroscopy of two complexes. The study of weak interactions is meaningful to provide supporting data for supramolecular chemistry theory and potential applications in molecular biology.
基金supported by the National Natural Science Foundation of China(No.20971004)the Natural Science Foundation of Anhui Provincial Education Commission(No.KJ2010A229)
文摘The reaction ofphenyl 2-pyridyl ketoxime （PhPyCNOH） with Cu（NO3）2·3H2O has led to a triangular complex Cu3（OH）（PhPyCNO）3（NO3）·NO3·H2O 1 containing the [Cu3（μ2-OH）]5＋ core and possessing the very rare inverse 9-metallacrown-3 motif created by the bridging oximate groups. Crystallographic data for 1： C36H30N8O11CU3, Mr = 941.30, monoclinic, space group C2/c, a = 18.815（9）, b = 33.888（15）, c = 14.307（7） A, β = 118.945（6）°, V= 7983（6） A3, Z = 8, Dc = 1.566 g/cm3, μ = 1.652 mm^-1, F（000） = 3816, R= 0.0644 and wR= 0.1393 for 3468 observed reflections （I〉 2σ（I））. Preliminary variable-temperature magnetic susceptibility studies reveal an antiferromagnetically-coupled system showing antisymmetrie exchange.
