Assembly of heterobimetallic NiII-LnIII (LnIII=DyIII, TbIII, GdIII, HoIII, ErIII, YIII) complexes using a ferrocene ligand: slow relaxation of the magnetization in DyIII, TbIII and HoIII analogues

被引:29
作者
Chakraborty, Amit [1 ]
Bag, Prasenjit [1 ]
Riviere, Eric [2 ]
Mallah, Talal [2 ]
Chandrasekhar, Vadapalli [1 ,3 ]
机构
[1] Indian Inst Technol, Dept Chem, Kanpur 208016, Uttar Pradesh, India
[2] Univ Paris 11, Inst Chim Mol & Mat Orsay, F-91405 Orsay, France
[3] Natl Inst Sci Educ & Res, Bhubaneswar 751005, Odisha, India
关键词
SINGLE-MOLECULE MAGNET; NEAR-INFRARED LUMINESCENCE; NI-II; DINUCLEAR COMPLEXES; SUPPORTED LIGANDS; ZERO-FIELD; FAMILY; LN; ANISOTROPY; TRINUCLEAR;
D O I
10.1039/c4dt00209a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A family of dinuclear 3d 4f heterobimetallic complexes [LNi(H2O)(mu-OAc)Ln(NO3)(2)]center dot CH3CN; {Ln=Dy-III (1), Tb-III (2), Ho-III (3), Gd-III (4), Er-III (5), Y-III (6)} have been synthesized by utilizing a ferrocene-based, dual compartmental ligand H2L. 1-6 are isostructural and crystallize in the triclinic (P (1) over bar) space group. In these complexes Ni-II is present in the inner coordination sphere of the dianionic [L](2-) ligand; Ln(III) is encapsulated in the outer coordination pocket. Ni-II shows a 2N, 4O coordination environment in a distorted octahedral geometry, while the LnIII ion possesses a 9O coordination environment in a distorted tricapped trigonal prismatic geometry. ESI-MS studies suggest that the structural integrity of 1-6 is retained in solution. Electrochemical studies reveal that these complexes show a reversible one-electron response typical of the ferrocene motif along with an irreversible one-electron oxidation involving the NiII/NiIII couple. Magnetic studies revealed the presence of ferromagnetic exchange coupling between NiII and LnIII centers as shown by the increase of chi M-T value upon cooling below 50 K for compounds 1, 2, 4 and 5. Further, dynamic magnetic susceptibility measurements (1-3) confirm the absence of an out-of-phase (chi'') signal at zero dc fields. However, when these measurements were carried out at 1000 Oe dc field the chi'' signal was observed, although maxima could not be detected up to 2 K.
引用
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页码:8921 / 8932
页数:12
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