Issue 2, 2012

Antiferromagnetic coupling across a tetrametallic unit through noncovalent interactions

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

Supplementary files

Article information

Article type
Edge Article
Submitted
25 Aug 2011
Accepted
05 Nov 2011
First published
17 Nov 2011

Chem. Sci., 2012,3, 602-609

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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