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
Two title compounds, 4,4?diformyl-diphenoxyethane (compound 1, C16H14O4) and 4,4?4创-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichlo...Two title compounds, 4,4?diformyl-diphenoxyethane (compound 1, C16H14O4) and 4,4?4创-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris(2-chloroethyl)amine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ? b = 105.823(6)? V = 675.7(2) 3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, m(MoKa) = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ? b = 99.505(1)? V = 2383.5(3) ?, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, m(MoKa) = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 (dialdehyde) is located at the crystallographic inversion center nearby the midpoint of C(8)C(8A) single bond. The three chains in the molecule of compound 2 (trialdehyde) are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.展开更多
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.
基金The authors thank the financial support of the Natural Science Foundation of Fujian Province (No. E0110010)
文摘Two title compounds, 4,4?diformyl-diphenoxyethane (compound 1, C16H14O4) and 4,4?4创-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris(2-chloroethyl)amine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ? b = 105.823(6)? V = 675.7(2) 3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, m(MoKa) = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ? b = 99.505(1)? V = 2383.5(3) ?, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, m(MoKa) = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 (dialdehyde) is located at the crystallographic inversion center nearby the midpoint of C(8)C(8A) single bond. The three chains in the molecule of compound 2 (trialdehyde) are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.
