Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 4, 2018
Previous Article Next Article

Theoretical evidence for the direct 3MLCT-HS deactivation in the light-induced spin crossover of Fe(ii)–polypyridyl complexes

Author affiliations

Abstract

Spin–orbit couplings have been calculated in twenty snapshots of a molecular dynamics trajectory of [Fe(bpy)3]2+ to address the importance of geometrical distortions and second-order spin–orbit coupling on the intersystem crossing rate constants in the light-induced spin crossover process. It was found that the effective spin–orbit coupling between the 3MLCT and 5T2 state is much larger than the direct coupling in the symmetric structure, which opens the possibility of a direct 3MLCT–5T2 deactivation without the intervention of triplet metal-centered states. Based on the calculated deactivation times, we conclude that both the direct pathway and the one involving intermediate triplet states are active in the ultrafast population of the metastable HS state, bringing in agreement two experimental observations that advocate for either deactivation mechanism. This resolves a long-standing dispute about the deactivation mechanism of Fe(II)–polypyridyl complexes in particular, and about light-induced magnetism in transition metal complexes in general.

Graphical abstract: Theoretical evidence for the direct 3MLCT-HS deactivation in the light-induced spin crossover of Fe(ii)–polypyridyl complexes

Back to tab navigation

Supplementary files

Article information


Submitted
13 Dec 2017
Accepted
22 Dec 2017
First published
05 Jan 2018

Phys. Chem. Chem. Phys., 2018,20, 2351-2355
Article type
Paper

Theoretical evidence for the direct 3MLCT-HS deactivation in the light-induced spin crossover of Fe(II)–polypyridyl complexes

C. Sousa, M. Llunell, A. Domingo and C. de Graaf, Phys. Chem. Chem. Phys., 2018, 20, 2351
DOI: 10.1039/C7CP08098K

Social activity

Search articles by author

Spotlight

Advertisements