A new lanthanide complex [Sm（C2O4）（H2O）5]nCln·2nH2O has been obtained by hydrothermal synthetic method. The crystal belongs to monoclinic, space group P21/n, with a = 7.5438（6）, b = 14.3201（11）, c = 10.8...A new lanthanide complex [Sm（C2O4）（H2O）5]nCln·2nH2O has been obtained by hydrothermal synthetic method. The crystal belongs to monoclinic, space group P21/n, with a = 7.5438（6）, b = 14.3201（11）, c = 10.8608（9）A, β = 94.565（4）°, V = 1169.55（16）A^3, C2H14ClO11Sm, Mr = 399.93, Z = 4, Dc = 2.271 g/cm^3, μ = 5.290 cm^-1, F（000） = 772, the final R = 0.0271 and wR = 0.0632 for 1880 observed reflections with I 〉 2σ（I）. X-ray crystal analysis reveals that each Sm（III） atom is nine-coordinated by four oxygen atoms from two oxalate ligands and five coordinated water molecules in a distorted tricapped trigonal prism. The chain-like structure of lanthanide oxalate is reported for the first time. The fluorescent property and magnetic behavior of the title compound were investigated. The θ of –14.3（2）° and J of –0.26 cm^-1 indicate antiferromagnetic interaction in the molecule.展开更多
The reaction of DyCl_(3)·6H_(2)O with a rigid diacylhydrazone ligand(H_(2)L)afforded a trinuclear precursor[Dy_(3)L_(2)Cl_(3)(H_(2)O)_(2)(CH_(3)OH)]Cl_(2)·3CH_(3)OH(1).The replacement of the Cl-ions and the ...The reaction of DyCl_(3)·6H_(2)O with a rigid diacylhydrazone ligand(H_(2)L)afforded a trinuclear precursor[Dy_(3)L_(2)Cl_(3)(H_(2)O)_(2)(CH_(3)OH)]Cl_(2)·3CH_(3)OH(1).The replacement of the Cl-ions and the coordinating solvents by the aryloxides ligands(Lx)-yields three trinuclear complexes[Dy_(3)L_(2)(Lx)_(5)]·nsol(x=1,2-naphthol(2);x=2,7-hydroxycoumarin(3);and x=3,phenol(4)).In complexes 2-4,two end Dy^(3+)centers adopt almost identical N_(4)O_(4) coordination sphere of D6h geometry while the central one adopts N_(4)O_(5) coordination sphere in Cs geometry.Magnetic measurements reveal weak antiferromagnetic interactions in the hydrated samples 2e-4e and two-step slow relaxation process under zero dc field with effective energy barriers Ueff of 439 and 91 K,353 and 40 K,466 and 89 K for SR and FR in 2e-4e,respectively.Such dynamic magnetic behaviour for 4 persists in the magnetically diluted sample of 4@Y.Complex 4 possesses the short Dy-O_(aryloxide) bond distance of 2.055(18)Å,and the largest Ueff among the reported linear trinuclear dysprosium complexes.Moreover,the functionalized aryloxides ligands(Lx)-show photoluminescence via intramolecular energy transfer,making 2e-4e luminescent Dy^(3+)SMMs with high energy barriers.展开更多
基金This work was supported by the NNSFC (20131020)the NSF for Distinguished Yong Scientist of China (20425104)the NSF of Fujian Province (E0510028)
文摘A new lanthanide complex [Sm（C2O4）（H2O）5]nCln·2nH2O has been obtained by hydrothermal synthetic method. The crystal belongs to monoclinic, space group P21/n, with a = 7.5438（6）, b = 14.3201（11）, c = 10.8608（9）A, β = 94.565（4）°, V = 1169.55（16）A^3, C2H14ClO11Sm, Mr = 399.93, Z = 4, Dc = 2.271 g/cm^3, μ = 5.290 cm^-1, F（000） = 772, the final R = 0.0271 and wR = 0.0632 for 1880 observed reflections with I 〉 2σ（I）. X-ray crystal analysis reveals that each Sm（III） atom is nine-coordinated by four oxygen atoms from two oxalate ligands and five coordinated water molecules in a distorted tricapped trigonal prism. The chain-like structure of lanthanide oxalate is reported for the first time. The fluorescent property and magnetic behavior of the title compound were investigated. The θ of –14.3（2）° and J of –0.26 cm^-1 indicate antiferromagnetic interaction in the molecule.
基金This work was supported by the National Natural Science Foundation of China(21971142,21973046 and 22271171).
文摘The reaction of DyCl_(3)·6H_(2)O with a rigid diacylhydrazone ligand(H_(2)L)afforded a trinuclear precursor[Dy_(3)L_(2)Cl_(3)(H_(2)O)_(2)(CH_(3)OH)]Cl_(2)·3CH_(3)OH(1).The replacement of the Cl-ions and the coordinating solvents by the aryloxides ligands(Lx)-yields three trinuclear complexes[Dy_(3)L_(2)(Lx)_(5)]·nsol(x=1,2-naphthol(2);x=2,7-hydroxycoumarin(3);and x=3,phenol(4)).In complexes 2-4,two end Dy^(3+)centers adopt almost identical N_(4)O_(4) coordination sphere of D6h geometry while the central one adopts N_(4)O_(5) coordination sphere in Cs geometry.Magnetic measurements reveal weak antiferromagnetic interactions in the hydrated samples 2e-4e and two-step slow relaxation process under zero dc field with effective energy barriers Ueff of 439 and 91 K,353 and 40 K,466 and 89 K for SR and FR in 2e-4e,respectively.Such dynamic magnetic behaviour for 4 persists in the magnetically diluted sample of 4@Y.Complex 4 possesses the short Dy-O_(aryloxide) bond distance of 2.055(18)Å,and the largest Ueff among the reported linear trinuclear dysprosium complexes.Moreover,the functionalized aryloxides ligands(Lx)-show photoluminescence via intramolecular energy transfer,making 2e-4e luminescent Dy^(3+)SMMs with high energy barriers.
