Please use this identifier to cite or link to this item:
Title: Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study
Author: Tezgerevska, Tina
Rousset, Elodie
Gable, Robert W.
Jameson, Guy N. L.
Sañudo Zotes, Eva Carolina
Starikova, Alyona A.
Boskovic, Colette
Keywords: Complexos metàl·lics
Metal complexes
Issue Date: 24-Jun-2019
Publisher: Royal Society of Chemistry
Abstract: Compounds [Co(L-N4R2)(dbdiox)](BPh4) (L-N4R2 = N,N′-di-alkyl-2,11-diaza[3.3]-(2,6)pyridinophane, R = iPr (1a), Et (2a); dbdiox = 3,5-di-tert-butyldioxolene) and [M(L-N4iPr2)(dbdiox)](BPh4) (M = Mn (3a), Fe (4a)) have been synthesized and investigated with a view to possible valence tautomeric (VT) or spin crossover (SCO) interconversions. Single crystal X-ray diffraction data for all compounds at 100 or 130 K indicate trivalent metal cations and di-tert-butylcatecholate (dbcat2−) dioxolene ligands. Variable temperature magnetic susceptibility data for all species between 2 and 340 K are consistent with these redox states, with low spin configurations for the cobalt(III) ions and high spin for the manganese(III) and iron(III) ions. Above 340 K, compound 1a exhibits an increase in magnetic susceptibility, suggesting the onset of a VT interconversion from low spin Co(III)-dbcat to high spin Co(II)-dbsq (dbsq− = di-tert-butylsemiquinonate) that is incomplete up to 400 K. In solution, variable temperature electronic absorption spectra and Evans NMR method magnetic susceptibility data indicate reversible VT interconversions for 1a in several solvents, with the transition temperature varying with solvent. Variable temperature electronic absorption spectra are temperature-invariant for 3a and 4a, while spectra for 2a in 1,2-dichloroethane suggest the onset of a VT transition at the highest temperatures measured. Density functional theory calculations on all four compounds and literature analogues provide key insights into the relative energies of the different electromeric forms and the possibilities for VT versus SCO interconversions in this family of compounds.
Note: Versió postprint del document publicat a:
It is part of: Dalton Transactions, 2019, vol. 48, num. 31, p. 11674-11689
Related resource:
ISSN: 1477-9226
Appears in Collections:Articles publicats en revistes (Química Inorgànica i Orgànica)

Files in This Item:
File Description SizeFormat 
691143.pdf1.49 MBAdobe PDFView/Open

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.