The copper(Ⅱ) DPP adduct Cu(DPP)(DMF)2(H2O)-(ClO4)2 1 (DPP = 4,7-diphenyl-1, 10-phentheanthroline, DMF = N,N'-dimethyl formamide) has been prepared by a direct synthetic method and structurally character...The copper(Ⅱ) DPP adduct Cu(DPP)(DMF)2(H2O)-(ClO4)2 1 (DPP = 4,7-diphenyl-1, 10-phentheanthroline, DMF = N,N'-dimethyl formamide) has been prepared by a direct synthetic method and structurally characterized. It presents a mononuclear structure and crystallizes in triclinic, space group P1 with a = 9.8717(2), b = 12.579, c = 14.7574(2) A, α = 67.976(6),β = 82.031(9), γ = 80.343(9)°, V = 1668.96(9)A, Z = 1, Dc= 1.495 g/cm^3,/t(MoKα) = 0.877 mm^-1, F(000) = 774, C60H64Cl4Cu2N8O221 Mr = 1502.09, the final R1= 0.0643 and wR2 = 0.1799 for 6153 observed reflections with 1 〉 2σ(1). Structure analysis shows that copper atom presents an unusual fivecoordination of square pyramid geometry. The whole structure is stabilized by π-π stacking interactions and static attractive forces from [ClO4]-anions. Based on crystal data, quantum chemistry calculation on DFF/B3LPY level was used to reveal the electronic structure of 1.展开更多
The new complex of [Sm(p-MOBA)3bath]2·4H2O (p-MOBA, p-methoxybenzoate; bath, 4,7-diphenyl-l,10- phenanthroline) was synthesized and characterized by elemental analysis, molar conductance, IR, UV and XRD patte...The new complex of [Sm(p-MOBA)3bath]2·4H2O (p-MOBA, p-methoxybenzoate; bath, 4,7-diphenyl-l,10- phenanthroline) was synthesized and characterized by elemental analysis, molar conductance, IR, UV and XRD patterns. The thermal decomposition of the complex was studied under the non-isothermal condition by TG-DTG and IR techniques. The most probable mechanism function of the dehydration process was obtained from the analysis of DSC curves of the complex employing the double extrapolated method on the basis of integral isoconversional non-linear (NL-INT) and Tang-Wanjun integral equations. The integral function of the mechanism was [1 -- (1 -α/2]1/2 and the corresponding kinetic parameters (activation energy E and the pre-exponential factor A) were obtained.展开更多
The polymerization behaviors of Styrene (St) in the presence of CuX/L [X=Cl or Br; L= 2,2 bipyridine (bpy), 1,10 phenanthroline (phen) or 4,7 diphenyl 1,10 phenanthroline (DPP) ] and R X (R=trichloromethyl, benz...The polymerization behaviors of Styrene (St) in the presence of CuX/L [X=Cl or Br; L= 2,2 bipyridine (bpy), 1,10 phenanthroline (phen) or 4,7 diphenyl 1,10 phenanthroline (DPP) ] and R X (R=trichloromethyl, benzyl or allyl; X=Cl or Br) have been studied and examined. In a CuCl/bpy/RCl/St system, a bimodal GPC peak at the early stage of polymerization was observed, and a concept of multi active species was proposed to explain this phenomenon. In a CuCl/phen (DPP)/RCl/St system, the \%M\%\-n of polystyrene (PS) increased linearly with St conversion and ln[M] o/[M] also increased linearly with time, indicating the living nature of this system. Furthermore, the stability of the propagating active species in a CuBr/phen/RBr/St system is higher than that in the CuBr/phen/RBr/St system.展开更多
基金This work was supported by the Foundation of Education Committee of Fujian Province (NOS: JB03052, JB04016, JB04017) and the Student Research Training Program (SRTP)(NOS:03100)
文摘The copper(Ⅱ) DPP adduct Cu(DPP)(DMF)2(H2O)-(ClO4)2 1 (DPP = 4,7-diphenyl-1, 10-phentheanthroline, DMF = N,N'-dimethyl formamide) has been prepared by a direct synthetic method and structurally characterized. It presents a mononuclear structure and crystallizes in triclinic, space group P1 with a = 9.8717(2), b = 12.579, c = 14.7574(2) A, α = 67.976(6),β = 82.031(9), γ = 80.343(9)°, V = 1668.96(9)A, Z = 1, Dc= 1.495 g/cm^3,/t(MoKα) = 0.877 mm^-1, F(000) = 774, C60H64Cl4Cu2N8O221 Mr = 1502.09, the final R1= 0.0643 and wR2 = 0.1799 for 6153 observed reflections with 1 〉 2σ(1). Structure analysis shows that copper atom presents an unusual fivecoordination of square pyramid geometry. The whole structure is stabilized by π-π stacking interactions and static attractive forces from [ClO4]-anions. Based on crystal data, quantum chemistry calculation on DFF/B3LPY level was used to reveal the electronic structure of 1.
基金Project supported by the National Natural Science Foundation of China (Nos. 21073053, 21073052 and 20773034), the Natural Science Foundation of Hebei Province (Nos. B2007000237, E2009000307) and Education Department Scientic Research Fund from Hebei Province (No. 2008469).
文摘The new complex of [Sm(p-MOBA)3bath]2·4H2O (p-MOBA, p-methoxybenzoate; bath, 4,7-diphenyl-l,10- phenanthroline) was synthesized and characterized by elemental analysis, molar conductance, IR, UV and XRD patterns. The thermal decomposition of the complex was studied under the non-isothermal condition by TG-DTG and IR techniques. The most probable mechanism function of the dehydration process was obtained from the analysis of DSC curves of the complex employing the double extrapolated method on the basis of integral isoconversional non-linear (NL-INT) and Tang-Wanjun integral equations. The integral function of the mechanism was [1 -- (1 -α/2]1/2 and the corresponding kinetic parameters (activation energy E and the pre-exponential factor A) were obtained.
文摘The polymerization behaviors of Styrene (St) in the presence of CuX/L [X=Cl or Br; L= 2,2 bipyridine (bpy), 1,10 phenanthroline (phen) or 4,7 diphenyl 1,10 phenanthroline (DPP) ] and R X (R=trichloromethyl, benzyl or allyl; X=Cl or Br) have been studied and examined. In a CuCl/bpy/RCl/St system, a bimodal GPC peak at the early stage of polymerization was observed, and a concept of multi active species was proposed to explain this phenomenon. In a CuCl/phen (DPP)/RCl/St system, the \%M\%\-n of polystyrene (PS) increased linearly with St conversion and ln[M] o/[M] also increased linearly with time, indicating the living nature of this system. Furthermore, the stability of the propagating active species in a CuBr/phen/RBr/St system is higher than that in the CuBr/phen/RBr/St system.