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Issue 37, 2013
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Ferrocene-based compartmental ligand for the assembly of neutral ZnII/LnIII heterometallic complexes

Vadapalli Chandrasekhar,*ab  Amit Chakrabortya  and  E. Carolina Sañudoc 
Author affiliations

* Corresponding authors

a Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India
E-mail: vc@tifrh.res.in, vc@iitk.ac.in

b Tata Institute of Fundamental Research, Centre for Interdisciplinary Sciences, 21 Brundavan Colony, Narsingi, Hyderabad-500075, India

c Departament de Química Inorgànica i Institut de Nanociència i Nanotecnologia, Universitat de Barcelona, Diagonal 645, 08028 Barcelona, Spain

Abstract

A ferrocene-based compartmental ligand, H2L, was synthesized by the reaction of diacetyl ferrocene with hydrazine hydrate followed by a condensation reaction with o-vanillin. [L]2− possesses a dual coordination pocket, an inner pocket of 2 imino nitrogens and two phenolate oxygens and an outer pocket of two phenolate and two methoxy oxygen atoms. Utilizing this ligand, several ZnII/LnIII heterobimetallic complexes were assembled: [LZn(μ-OAc)Dy(NO3)2] (2), [LZn(μ-OAc)Tb(NO3)2] (3), [LZn(μ-OAc)Gd(NO3)2·2CHCl3] (4), [LZn(μ-OAc)Er(NO3)2] (5), [LZn(μ-OAc)Ho(NO3)2] (6), [LZn(μ-OAc)Eu(NO3)2] (7). All of these metal complexes are neutral and isostructural: the ZnII ion occupies the inner coordination pocket while the LnIII ion occupies the outer coordination pocket of the doubly deprotonated ligand [L]2−. Zn(II) has a coordination number of 5 (2N, 3O) in a square pyramidal coordination geometry while Ln(III) has a coordination number of 9 (9O) in a distorted tricapped trigonal prismatic geometry. Zn(II) and the 4f metal ion are bridged to each other by two phenolate oxygen atoms and an acetate ligand. ESI-MS reveals that 2–7 retain their structural integrity in solution. Cyclic voltammetry of 1–7 revealed a quasi-reversible oxidation (involving the ferrocene motif) and an irreversible reduction of the hydrazone unit. Magnetic studies of 2, 3 and 6 were carried out. Ac susceptibility studies did not reveal slow relaxation of magnetization.

Graphical abstract: Ferrocene-based compartmental ligand for the assembly of neutral ZnII/LnIII heterometallic complexes

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Publication details

The article was received on 01 Jun 2013, accepted on 01 Jul 2013 and first published on 01 Jul 2013


Article type: Paper
DOI: 10.1039/C3DT51432C
Citation: Dalton Trans., 2013,42, 13436-13443
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    Ferrocene-based compartmental ligand for the assembly of neutral ZnII/LnIII heterometallic complexes

    V. Chandrasekhar, A. Chakraborty and E. C. Sañudo, Dalton Trans., 2013, 42, 13436
    DOI: 10.1039/C3DT51432C

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