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Ultrafast, reversible intersystem crossing (ISC) is reported under ambient conditions for the electronic ground state of the pentacoordinate cobalt nitrosyl complexes, [CoX2(NO)(PMePh2)2] (X = Cl, Br), in solution. ISCs on such short timescales are more typically observed in electronically excited states reached by absorption of ultraviolet or visible light. Singlet and triplet electron spin states of the complex, corresponding to two different isomers, are populated at room temperature, and the two isomers exchange on a timescale of a few picoseconds. Ultrafast two-dimensional infra-red spectroscopy observes the change in wavenumber of the NO ligand band accompanying the isomerization and associated ISC on the (spin) adiabatic ground potential energy surface. Comparison of the dynamics of the chloro- and bromo-complexes shows that inertial effects of the ligand motion have a greater effect than spin-orbit coupling on determining the forward and reverse isomerization and ISC rates.
- INTERSYSTEM CROSSING
- ULTRAFAST DYNAMICS
- ELECTRON SPIN
Marroux, H., Curchod, B., Faradji, C., Shuttleworth, T., Sparkes, H., Pringle, P., & Orr-Ewing, A. (2017). Spin changes accompany ultrafast structural interconversion in the ground state of a cobalt nitrosyl complex. Angewandte Chemie - International Edition, 56(44), 13713-13716. https://doi.org/10.1002/anie.201707508