The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of...The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of Dy_(2)(L_1)_(2)(L_(2))_(2)(CH_(3)OH)_(2)·CH_(2)Cl_(2)·CH_(3)OH(1) and Dy_(2)(L_1)_(2)(L_(3))_(2)(CH_(3)OH)_(2)·CH_(3)CN(2),where L_1,L_(2) and L_(3) represent the deprotonated form of 4-tert-butyl-2-(7-methoxybenzo[d]oxazol-2-yl)phenol,(E)-1-(((3,5-di-tert-butyI-2-hydroxyphenyI)imino)methyl)naphthalen-2-ol and(E)-2,4-di-tertbutyl-6-((2-hydroxybenzylidene)amino)phenol.The tiny difference of the core structure of 1 and 2 is derived from the steric hindrance of Schiff base ligands L_(2) and L_(3).Dynamic magnetic measurements reveal that 1 and 2 show frequency-dependent out-of-phase alternating-current susceptibility signal peaks at different temperatures under zero dc field,diagnostic of single-molecule magnet behavior.The experimental derived energy barrier to magnetization reversal for 1 and 2 is 108(1),47(2) and 33(3) K.Ab initio CASSCF calculations performed on 1 and 2 suggest that the origin of the difference in magnetic properties originates from the variation in the single-ion anisotropy that arises due to minor structural variation.Further,the equation to calculate the effective energy barrier for Dy_(2) proposed earlier is found to yield an excellent agreement with the experimental results.Solid state fluorescence measurements performed on 1 and 2 demonstrate that both exhibit two ligands centered components of fluorescent emissive,in addition,with different emitting colors and chromaticity coordinates.The discrepancy of fluorescence and single molecule magnet behavior showed by 1 and 2 can be attributed to the steric hindrance effect of Schiff base ligands.展开更多
A dinuclear dysprosium（III） complex with benzoic acid and 1,10-phenanthroline, [Dy（BA）3phen]2 （BA = benzoate, PHEN = 1,10-phenanthroline） （C66H46Dy2NaO12, Mr = 1412.07） was synthesized and characterized by ele...A dinuclear dysprosium（III） complex with benzoic acid and 1,10-phenanthroline, [Dy（BA）3phen]2 （BA = benzoate, PHEN = 1,10-phenanthroline） （C66H46Dy2NaO12, Mr = 1412.07） was synthesized and characterized by elemental analysis, UV, IR, X-ray diffraction, molar conductance and TG-DTG techniques. It crystallizes in triclinic, space group P1 with a = 10.773（2）, b = 11.933（3）, c = 12.417（5） A, α= 105.226（3）,β= 93.470（3）, γ= 113.475（2）°, V= 1388.0（7）, Z = 1, Dc = 1.689 g/cm3, μ（MoKa） = 2.742 mm-1 and F（000） = 698. R = 0.0210, wR = 0.0538. In the crystal, each Dy（III） ion is eight-coordinated by one bidentate chelating carboxylate group, four bidentate bridging carboxylate groups and one 1,10-phenanthroline molecule. The thermal decomposition process of [Dy（BA）3phen]2 has been determined by thermal analysis.展开更多
Crystal structures of neodymium (III) and dysprosium (III) nitrate complexes with the new ligand N, N’-dimethyl-N, N’-diphenyladipamide (mpaa) has been determined. Both complexes are triclinic with space group Pī, ...Crystal structures of neodymium (III) and dysprosium (III) nitrate complexes with the new ligand N, N’-dimethyl-N, N’-diphenyladipamide (mpaa) has been determined. Both complexes are triclinic with space group Pī, formula [C22H30N5NdO12S]2 1 [C42H54N7DyO14S 2] Mr = 1465.62[1075.48], a = 8.541(1)[9.711(2)], b = 11.915(1)[16.017(3)], c = 15.906(1) [16.686(3)] ?, α =107.22(1)[109.600(1)], β = 98.12(1)[92.50(1)], γ = 99.78(1) [96.22(1)]°, V = 1491.8(2)[2421.7(8)] ?3, Dc = 1.631[1.475] g·cm-3, Z = 1[2], F(000) = 738[1098], μ=0.71073cm-1; R=0.0261[0.0364], wR=0.0611[0.0857] reflections with I>2σ(I). Complex (1) is dinuclear, in which two Nd(III) ions are double-bridged by two mpaa ligands. And Dy(mpaa)2(dmso)(NO3)3 (2) (dmso= dimethylsulfoxide) is a mononuclear complex, in which one of the two C=O groups in MPAA is uncoordinated. In the two above complexes, each Ln(III) ion is nine-coordinated including three bidenate nitrates, one dmso molecule and two carbonyl oxygens from two different mpaa ligands. Neutral monodentate dmso enters the coordination sphere to meet the geometric requirements. When the number of methylene between O=C…C=O in diamides of the type (R1R2NCO)2(CH2)n was increased, the ligand prefers to act as a bridging reagent rather than a chelate.展开更多
The title complexes [Dy（p-NBA）3Phen]2-3H2O（Ⅰ） and [Dy（m-NBA）3Phen]2·4H2O（Ⅱ） were synthesized, in the two molecular formulas of which NBA is nitrobenzoate and Phen is 1,10-phenanthroline. The characteriz...The title complexes [Dy（p-NBA）3Phen]2-3H2O（Ⅰ） and [Dy（m-NBA）3Phen]2·4H2O（Ⅱ） were synthesized, in the two molecular formulas of which NBA is nitrobenzoate and Phen is 1,10-phenanthroline. The characterizations of the complexes were carried out by means of elemental analysis, UV, IR, XRD and molar conductivity. The thermal decomposition of the two complexes were studied under the non-isothermal condition by DSC, TG-DTG and IR methods in detail. The kinetic parameters of the dehydration process were also obtained by the analysis of DSC curves of the two complexes with Popescu and Vyazovkin methods, respectively.展开更多
基金Project supported by National Natural Science Foundation of China (21601143)Natural Science Foundation of Shaanxi Province (2021JM309)+2 种基金Open Funds of the State Key Laboratory of Rare Earth Resource of Changchun Institute of Applied Chemistry (RERU2021012)Science and Technology Innovation Team Program of Shaanxi Province (2022TD-32) and DST/SERB (CRG/2018/000430,DST/SJF/CSA03/2018-10SB/SJF/2019-20/12)。
文摘The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of Dy_(2)(L_1)_(2)(L_(2))_(2)(CH_(3)OH)_(2)·CH_(2)Cl_(2)·CH_(3)OH(1) and Dy_(2)(L_1)_(2)(L_(3))_(2)(CH_(3)OH)_(2)·CH_(3)CN(2),where L_1,L_(2) and L_(3) represent the deprotonated form of 4-tert-butyl-2-(7-methoxybenzo[d]oxazol-2-yl)phenol,(E)-1-(((3,5-di-tert-butyI-2-hydroxyphenyI)imino)methyl)naphthalen-2-ol and(E)-2,4-di-tertbutyl-6-((2-hydroxybenzylidene)amino)phenol.The tiny difference of the core structure of 1 and 2 is derived from the steric hindrance of Schiff base ligands L_(2) and L_(3).Dynamic magnetic measurements reveal that 1 and 2 show frequency-dependent out-of-phase alternating-current susceptibility signal peaks at different temperatures under zero dc field,diagnostic of single-molecule magnet behavior.The experimental derived energy barrier to magnetization reversal for 1 and 2 is 108(1),47(2) and 33(3) K.Ab initio CASSCF calculations performed on 1 and 2 suggest that the origin of the difference in magnetic properties originates from the variation in the single-ion anisotropy that arises due to minor structural variation.Further,the equation to calculate the effective energy barrier for Dy_(2) proposed earlier is found to yield an excellent agreement with the experimental results.Solid state fluorescence measurements performed on 1 and 2 demonstrate that both exhibit two ligands centered components of fluorescent emissive,in addition,with different emitting colors and chromaticity coordinates.The discrepancy of fluorescence and single molecule magnet behavior showed by 1 and 2 can be attributed to the steric hindrance effect of Schiff base ligands.
基金Supported by NNSFC, NSF of Hebei Province (No. B2007000237)Hebei Education Department (No. 2004325)Hebei Normal University (No. L2006Z06 and L2005Y12)
文摘A dinuclear dysprosium（III） complex with benzoic acid and 1,10-phenanthroline, [Dy（BA）3phen]2 （BA = benzoate, PHEN = 1,10-phenanthroline） （C66H46Dy2NaO12, Mr = 1412.07） was synthesized and characterized by elemental analysis, UV, IR, X-ray diffraction, molar conductance and TG-DTG techniques. It crystallizes in triclinic, space group P1 with a = 10.773（2）, b = 11.933（3）, c = 12.417（5） A, α= 105.226（3）,β= 93.470（3）, γ= 113.475（2）°, V= 1388.0（7）, Z = 1, Dc = 1.689 g/cm3, μ（MoKa） = 2.742 mm-1 and F（000） = 698. R = 0.0210, wR = 0.0538. In the crystal, each Dy（III） ion is eight-coordinated by one bidentate chelating carboxylate group, four bidentate bridging carboxylate groups and one 1,10-phenanthroline molecule. The thermal decomposition process of [Dy（BA）3phen]2 has been determined by thermal analysis.
基金the Key Laboratory of Organic Synthesis, Jiangsu Province.
文摘Crystal structures of neodymium (III) and dysprosium (III) nitrate complexes with the new ligand N, N’-dimethyl-N, N’-diphenyladipamide (mpaa) has been determined. Both complexes are triclinic with space group Pī, formula [C22H30N5NdO12S]2 1 [C42H54N7DyO14S 2] Mr = 1465.62[1075.48], a = 8.541(1)[9.711(2)], b = 11.915(1)[16.017(3)], c = 15.906(1) [16.686(3)] ?, α =107.22(1)[109.600(1)], β = 98.12(1)[92.50(1)], γ = 99.78(1) [96.22(1)]°, V = 1491.8(2)[2421.7(8)] ?3, Dc = 1.631[1.475] g·cm-3, Z = 1[2], F(000) = 738[1098], μ=0.71073cm-1; R=0.0261[0.0364], wR=0.0611[0.0857] reflections with I>2σ(I). Complex (1) is dinuclear, in which two Nd(III) ions are double-bridged by two mpaa ligands. And Dy(mpaa)2(dmso)(NO3)3 (2) (dmso= dimethylsulfoxide) is a mononuclear complex, in which one of the two C=O groups in MPAA is uncoordinated. In the two above complexes, each Ln(III) ion is nine-coordinated including three bidenate nitrates, one dmso molecule and two carbonyl oxygens from two different mpaa ligands. Neutral monodentate dmso enters the coordination sphere to meet the geometric requirements. When the number of methylene between O=C…C=O in diamides of the type (R1R2NCO)2(CH2)n was increased, the ligand prefers to act as a bridging reagent rather than a chelate.
基金Supported by the National Natural Science Foundation of China(No.20773034)the Natural Science Foundation of Hebei Province,China(No.B2007000237)the Science Foundation of Hebei Normal University,China(No.L2006Z06)
文摘The title complexes [Dy（p-NBA）3Phen]2-3H2O（Ⅰ） and [Dy（m-NBA）3Phen]2·4H2O（Ⅱ） were synthesized, in the two molecular formulas of which NBA is nitrobenzoate and Phen is 1,10-phenanthroline. The characterizations of the complexes were carried out by means of elemental analysis, UV, IR, XRD and molar conductivity. The thermal decomposition of the two complexes were studied under the non-isothermal condition by DSC, TG-DTG and IR methods in detail. The kinetic parameters of the dehydration process were also obtained by the analysis of DSC curves of the two complexes with Popescu and Vyazovkin methods, respectively.
