Issue 44, 2019

Unconventional two-step spin relaxation dynamics of [Re(CO)3(im)(phen)]+ in aqueous solution


Changes of molecular spin are ubiquitous in chemistry and biology. Among spin flip processes, one of the fastest is intersystem crossing (ISC) in transition metal complexes. Here, we investigate the spin relaxation dynamics and emission spectrum of [Re(CO)3(im)(phen)]+ (im = imidazole, phen = phenanthroline) using extensive full-dimensional excited-state dynamics simulations in explicit aqueous solution. Contrary to what has been observed in other transition metal complexes, the transition from the singlet to triplet states occurs via a two-step process, with clearly separable electronic and nuclear-driven components with two different time scales. The initially excited electronic wave function is a “molecular spin–orbit wave packet” that evolves almost instantaneously, with an 8 fs time constant, into an approximate 25 : 75 singlet-to-triplet equilibrium. Surprisingly, this ISC process is an order of magnitude faster than it was previously documented for this and other rhenium(I) carbonyl diimine complexes from emission spectra. Simulations including explicit laser field interactions evidence that few-cycle UV laser pulses are required to follow the creation and evolution of such molecular spin–orbit wave packets. The analysis of the dynamics also reveals a retarded ISC component, with a time constant of 420 fs, which can be explained invoking intramolecular vibrational energy redistribution. The emission spectrum is shown to be characterized by ISC convoluted with internal conversion and vibrational relaxation. These results provide fundamental understanding of ultrafast intersystem crossing in transition metal complexes.

Graphical abstract: Unconventional two-step spin relaxation dynamics of [Re(CO)3(im)(phen)]+ in aqueous solution

Supplementary files

Article information

Article type
Edge Article
24 Jul 2019
19 Sep 2019
First published
27 Sep 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 10405-10411

Unconventional two-step spin relaxation dynamics of [Re(CO)3(im)(phen)]+ in aqueous solution

S. Mai and L. González, Chem. Sci., 2019, 10, 10405 DOI: 10.1039/C9SC03671G

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