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oai:recercat.cat:2445/1630272025-12-04T20:55:29Zcom_2072_1057col_2072_478796col_2072_478917

urn:hdl:2445/163027 Theoretical evidence for the direct 3MLCT-HS deactivation in the light-induced spin crossover of Fe(II)-polypyridyl complexes Sousa Romero, Carmen Llunell Marí, Miquel Domingo, Alex Graaf, Coen de Ferro Lligands Spin (Física nuclear) Iron Ligands Nuclear spin 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 path- way 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. 2020-05-29T09:00:03Z 2020-05-29T09:00:03Z 2018-01-05 2020-05-29T09:00:03Z info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Versió postprint del document publicat a: https://doi.org/10.1039/c7cp08098k Physical Chemistry Chemical Physics, 2018, vol. 20, num. 4, p. 2351-2355 https://doi.org/10.1039/c7cp08098k (c) Sousa Romero, Carmen et al., 2018 info:eu-repo/semantics/openAccess Royal Society of Chemistry Articles publicats en revistes (Ciència dels Materials i Química Física)