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Issue 11, 2013
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Double oxidation localizes spin in a Ni bis-phenoxyl radical complex

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Abstract

The electronic structure of a doubly oxidized Ni salen complex NiSaltBu (SaltBu = N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) has been investigated by both experimental and theoretical methods. The doubly oxidized product was probed by resonance Raman spectroscopy, UV-vis-NIR, and EPR to determine the locus of oxidation as well as the spectroscopic signature of the complex. It was determined that double oxidation of NiSaltBu affords a bis-ligand radical species in solution via the presence of phenoxyl radical bands at ν7a (1504 cm−1) and ν8a (1579 cm−1) in the Raman spectrum, and the loss of the intense NIR transition reported for the mono-radical complex (Angew. Chem., Int. Ed., 2007, 46, 5198). Spectroscopic experiments, complemented by DFT calculations, show that the two radical spins are predominantly localized on the phenolate moieties, in opposition to the extensive delocalization over the ligand framework observed for the mono-radical analogue.

Graphical abstract: Double oxidation localizes spin in a Ni bis-phenoxyl radical complex

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Publication details

The article was received on 03 Nov 2012, accepted on 06 Jan 2013 and first published on 07 Jan 2013


Article type: Paper
DOI: 10.1039/C2DT32632A
Citation: Dalton Trans., 2013,42, 3950-3956
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    Double oxidation localizes spin in a Ni bis-phenoxyl radical complex

    T. J. Dunn, M. I. Webb, K. Hazin, P. Verma, E. C. Wasinger, Y. Shimazaki and T. Storr, Dalton Trans., 2013, 42, 3950
    DOI: 10.1039/C2DT32632A

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