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Issue 11, 2015

A series of tetraazalene radical-bridged M2 (M = CrIII, MnII, FeII, CoII) complexes with strong magnetic exchange coupling

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Abstract

The ability of tetraazalene radical bridging ligands to mediate exceptionally strong magnetic exchange coupling across a range of transition metal complexes is demonstrated. The redox-active bridging ligand N,N′,N′′,N′′′-tetra(2-methylphenyl)-2,5-diamino-1,4-diiminobenzoquinone (NMePhLH2) was metalated to give the series of dinuclear complexes [(TPyA)2M2(NMePhL2−)]2+ (TPyA = tris(2-pyridylmethyl)amine, M = MnII, FeII, CoII). Variable-temperature dc magnetic susceptibility data for these complexes reveal the presence of weak superexchange interactions between metal centers, and fits to the data provide coupling constants of J = −1.64(1) and −2.16(2) cm−1 for M = MnII and FeII, respectively. One-electron reduction of the complexes affords the reduced analogues [(TPyA)2M2(NMePhL3−˙)]+. Following a slightly different synthetic procedure, the related complex [(TPyA)2CrIII2(NMePhL3−˙)]3+ was obtained. X-ray diffraction, cyclic voltammetry, and Mössbauer spectroscopy indicate the presence of radical NMePhL3−˙ bridging ligands in these complexes. Variable-temperature dc magnetic susceptibility data of the radical-bridged species reveal the presence of strong magnetic interactions between metal centers and ligand radicals, with simulations to data providing exchange constants of J = −626(7), −157(7), −307(9), and −396(16) cm−1 for M = CrIII, MnII, FeII, and CoII, respectively. Moreover, the strength of magnetic exchange in the radical-bridged complexes increases linearly with decreasing M–L bond distance in the oxidized analogues. Finally, ac magnetic susceptibility measurements reveal that [(TPyA)2Fe2(NMePhL3−˙)]+ behaves as a single-molecule magnet with a relaxation barrier of Ueff = 52(1) cm−1. These results highlight the ability of redox-active tetraazalene bridging ligands to enable dramatic enhancement of magnetic exchange coupling upon redox chemistry and provide a rare opportunity to examine metal–radical coupling trends across a transmetallic series of complexes.

Graphical abstract: A series of tetraazalene radical-bridged M2 (M = CrIII, MnII, FeII, CoII) complexes with strong magnetic exchange coupling

Supplementary files

Article information


Submitted
26 Jul 2015
Accepted
17 Aug 2015
First published
18 Aug 2015

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 6639-6648
Article type
Edge Article
Author version available

A series of tetraazalene radical-bridged M2 (M = CrIII, MnII, FeII, CoII) complexes with strong magnetic exchange coupling

J. A. DeGayner, I. Jeon and T. D. Harris, Chem. Sci., 2015, 6, 6639 DOI: 10.1039/C5SC02725J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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