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Issue 23, 2014
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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

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Abstract

A family of dinuclear 3d–4f heterobimetallic complexes [LNi(H2O)(μ-OAc)Ln(NO3)2]·CH3CN; {Ln = DyIII (1), TbIII (2), HoIII (3), GdIII (4), ErIII (5), YIII (6)} have been synthesized by utilizing a ferrocene-based, dual compartmental ligand H2L. 1–6 are isostructural and crystallize in the triclinic (P[1 with combining macron]) space group. In these complexes NiII is present in the inner coordination sphere of the dianionic [L]2− ligand; LnIII is encapsulated in the outer coordination pocket. NiII 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 χMT 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 (χ′′) signal at zero dc fields. However, when these measurements were carried out at 1000 Oe dc field the χ′′ signal was observed, although maxima could not be detected up to 2 K.

Graphical abstract: 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

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Publication details

The article was received on 23 Jan 2014, accepted on 05 Apr 2014 and first published on 15 Apr 2014


Article type: Paper
DOI: 10.1039/C4DT00209A
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Citation: Dalton Trans., 2014,43, 8921-8932

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    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

    A. Chakraborty, P. Bag, E. Rivière, T. Mallah and V. Chandrasekhar, Dalton Trans., 2014, 43, 8921
    DOI: 10.1039/C4DT00209A

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