Ultrafast Intersystem Crossing vs Internal Conversion in α-Diimine Transition Metal Complexes: Quantum Evidence

The Journal of Physical Chemistry Letters
Maria FumanalChantal Daniel

Abstract

Whereas third row transition metal carbonyl α-diimine complexes display luminescent properties and possess low-lying triplet metal-to-ligand charge transfer (MLCT) states efficiently accessible by a spin-vibronic mechanism, first row analogues hold low-lying metal-centered (MC) excited states that could quench these properties. Upon visible irradiation, different functions are potentially stimulated, namely, luminescence, electron transfer, or photoinduced CO release, the branching ratio of which is governed by the energetics, the character, and the early time dynamics of the photoactive excited states. Simulations of ultrafast nonadiabatic quantum dynamics, including spin-vibronic effects, of [M(imidazole)(CO)3(phenanthroline)]+ (M = Mn, Re) highlight the role of the metal atom. An ultrafast intersystem crossing process, driven by spin-orbit coupling, populates the low-lying triplet states of [Re(imidazole)(CO)3(phen)]+ within the first tens of fs. In contrast, efficient internal conversion between the two lowest 1MLCT states of [Mn(imidazole)(CO)3(phen)]+ is mediated within 50 fs by vibronic coupling with upper MC and MLCT states.

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Citations

Jan 5, 2019·Physical Chemistry Chemical Physics : PCCP·Inga S Ulusoy, Angela K Wilson
Sep 16, 2019·The Journal of Chemical Physics·Mátyás PápaiKlaus B Møller
Feb 29, 2020·Chemical Science·Sebastian Mai, Leticia González
Dec 15, 2020·Physical Chemistry Chemical Physics : PCCP·Chantal Daniel
Dec 16, 2020·Physical Chemistry Chemical Physics : PCCP·Torsha MoitraSwapan Chakrabarti
Apr 4, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·James A GreenFabrizio Santoro
Apr 24, 2021·The Journal of Chemical Physics·Maria FumanalEtienne Gindensperger
Oct 27, 2020·The Journal of Physical Chemistry. a·Gareth W Richings, Scott Habershon
Nov 6, 2020·The Journal of Physical Chemistry Letters·Maria Fumanal, Clémence Corminboeuf
Jul 25, 2019·Journal of Chemical Theory and Computation·Felix PlasserLeticia González
Sep 2, 2021·JACS Au·J Patrick Zobel, Leticia González
Sep 29, 2021·Physical Chemistry Chemical Physics : PCCP·G A FarrowN P Ernsting

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