Valence tautomerism versus spin crossover in pyridinophane-cobalt-dioxolene complexes: an experimental and computational study
| Autor: | Elodie Rousset, Guy N. L. Jameson, Tina Tezgerevska, Colette Boskovic, Alyona A. Starikova, Robert W. Gable, E. Carolina Sañudo |
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| Přispěvatelé: | Universitat de Barcelona |
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Valence (chemistry)
Absorption spectroscopy 010405 organic chemistry Chemistry chemistry.chemical_element Crystal structure 010402 general chemistry 01 natural sciences Tautomer Magnetic susceptibility Complexos metàl·lics 3. Good health 0104 chemical sciences Inorganic Chemistry Crystallography Spin crossover Metal complexes Density functional theory Cobalt |
| Zdroj: | Dipòsit Digital de la UB Universidad de Barcelona Recercat. Dipósit de la Recerca de Catalunya instname |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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