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Issue 11, 2015
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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

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Publication details

The article was received on 26 Jul 2015, accepted on 17 Aug 2015 and first published on 18 Aug 2015


Article type: Edge Article
DOI: 10.1039/C5SC02725J
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Chem. Sci., 2015,6, 6639-6648
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    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

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