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Issue 2, 2012
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Antiferromagnetic coupling across a tetrametallic unit through noncovalent interactions

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Abstract

Three paramagnetic heterobimetallic lantern complexes of the form [PtM(tba)4(OH2)] (M = Fe, 1; Co, 2; Ni, 3; tba = thiobenzoate) have been prepared in a single-step, bench-top procedure. In all three cases, a lantern structure with Pt–M bonding is observed in solution and in the solid state. Compound 1 is a monomer whereas 3 exists as a dimer in the solid state via a Pt⋯Pt metallophilic interaction. Compound 2 has been characterized in forms with (2a, purple) and without (2b, yellow) Pt⋯Pt metallophilic interactions. The dimers 2a (J = −10 cm−1, based on the spin Hamiltonian Ĥ = −2J(SA·SB)) and 3 (J = −60 cm−1) exhibit antiferromagnetic coupling between the two first-row metal ions in the solid state via a Pt⋯Pt non-covalent metallophilic interaction. The electronic structure of C4v [PtM(tba)4], C2 [PtM(tba)4(OH2)], (M = Fe, Co, Ni) and D2 symmetry [PtM(tba)4(OH2)]2 M = Co, Ni, units have been studied with DFT calculations, confirming the relative spin-state energies observed and the antiferromagnetic exchange pathway through four dz2 orbitals. The compounds 2a and 3 are the first examples of antiferromagnetic coupling through an unbridged M⋯M contact.

Graphical abstract: Antiferromagnetic coupling across a tetrametallic unit through noncovalent interactions

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Publication details

The article was received on 25 Aug 2011, accepted on 05 Nov 2011 and first published on 17 Nov 2011


Article type: Edge Article
DOI: 10.1039/C1SC00608H
Chem. Sci., 2012,3, 602-609

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    Antiferromagnetic coupling across a tetrametallic unit through noncovalent interactions

    E. W. Dahl, F. G. Baddour, S. R. Fiedler, W. A. Hoffert, M. P. Shores, G. T. Yee, J. Djukic, J. W. Bacon, A. L. Rheingold and L. H. Doerrer, Chem. Sci., 2012, 3, 602
    DOI: 10.1039/C1SC00608H

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