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TitleSingle-ion anisotropy and exchange coupling in cobalt(ii)-radical complexes: insights from magnetic and ab initio studies
Publication TypeJournal Article
Year of Publication2019
AuthorsGransbury, GK, Boulon, M-E, Mole, RA, Gable, RW, Moubaraki, B, Murray, KS, Sorace, L, Soncini, A, Boskovic, C
JournalCHEMICAL SCIENCE
Volume10
Pagination8855-8871
Date PublishedOCT 14
ISSN2041-6520
Abstract
{The concurrent effects of single-ion anisotropy and exchange interactions on the electronic structure and magnetization dynamics have been analyzed for a cobalt(ii)-semiquinonate complex. Analogs containing diamagnetic catecholate and tropolonate ligands were employed for comparison of the magnetic behavior and zinc congeners assisted with the spectroscopic characterization and assessment of intermolecular interactions in the cobalt(ii) compounds. Low temperature X-band (nu approximate to 9.4 GHz) and W-Band (nu approximate to 94 GHz) electron paramagnetic resonance spectroscopy and static and dynamic magnetic measurements have been used to elucidate the electronic structure of the high spin cobalt(ii) ion in [Co(Me(3)tpa)(Br(4)cat)] (1; Me(3)tpa = tris[(6-methyl-2-pyridyl)methyl]amine, Br(4)cat(2-) = tetrabromocatecholate) and [Co(Me(3)tpa)(trop)](PF6) (2(PF6); trop(-) = tropolonate), which show slow relaxation of the magnetization in applied field. The cobalt(ii)-semiquinonate exchange interaction in [Co(Me(3)tpa)(dbsq)](PF6)center dot tol (3(PF6)center dot tol; dbsq(-) = 3,5-di-tert-butylsemiquinonate
DOI10.1039/c9sc00914k
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