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Issue 44, 2016
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Windmill-shaped octanuclear ZnII4/LnIII4 (LnIII = Dy, Tb, Ho) heterometallic ensembles supported by a tetraferrocene scaffold

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Abstract

Utilizing a new ferrocene-based compartmental ligand, H4L (1), a series of novel heterometallic complexes [{LZn(μ-OAc)Dy}44-H2O)] (2), [{LZn(μ-OAc)Tb}44-H2O)] (3), [{LZn(μ-OAc)Ho}44-H2O)] (4), [L = Fe[(C5H4){–C(Me)[double bond, length as m-dash]N–N[double bond, length as m-dash]C6H3-(o-O)(m-O)}]2] were synthesized and characterized. 2 and 3 crystallize in the monoclinic crystal system in the I2/m space group, whereas 4 crystallizes in the tetragonal crystal system in the I4/m space group. The tetra deprotonated ligand L4− has two distinct coordination compartments: one pocket (2N, 2O) suitable for the transition metal (3d) ions and another pocket (4O) suitable for lanthanide (4f) metal ions. Additionally, the terminal phenoxo group can be utilized for cluster expansion. In all the complexes, the ZnII ion is in a perfect square pyramidal (2N, 3O) geometry whereas the lanthanide ion has a coordination number of eight (8O) in a distorted biaugmented trigonal-prism geometry. The electrochemical properties of 2 and 3 along with ligand H4L (1) were studied by cyclic voltammetry (CV). All the complexes display a similar type of electrochemical behavior viz., one quasi-reversible oxidation typical of a ferrocene/ferrocenium motif. The magnetic properties of all the complexes have also been investigated.

Graphical abstract: Windmill-shaped octanuclear ZnII4/LnIII4 (LnIII = Dy, Tb, Ho) heterometallic ensembles supported by a tetraferrocene scaffold

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Publication details

The article was received on 08 Aug 2016, accepted on 24 Sep 2016, published on 26 Sep 2016 and first published online on 26 Sep 2016


Article type: Paper
DOI: 10.1039/C6DT03144G
Citation: Dalton Trans., 2016,45, 17633-17643
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    Windmill-shaped octanuclear ZnII4/LnIII4 (LnIII = Dy, Tb, Ho) heterometallic ensembles supported by a tetraferrocene scaffold

    A. Chakraborty, J. Goura, P. Bag, A. K. Bar, J. Sutter and V. Chandrasekhar, Dalton Trans., 2016, 45, 17633
    DOI: 10.1039/C6DT03144G

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