Spin Changes Accompany Ultrafast Structural Interconversion in the Ground State of a Cobalt Nitrosyl Complex

Marroux, Hugo J.B.; Curchod, Basile F.E.; Faradji, Charly A.; Shuttleworth, Timothy A.; Sparkes, Hazel A.; Pringle, Paul G.; Orr-Ewing, Andrew J.

doi:10.1002/anie.201707508

Spin Changes Accompany Ultrafast Structural Interconversion in the Ground State of a Cobalt Nitrosyl Complex

Marroux, Hugo J.B.; Curchod, Basile F.E.; Faradji, Charly A.; Shuttleworth, Timothy A.; Sparkes, Hazel A.; Pringle, Paul G.; Orr-Ewing, Andrew J.

Authors

Hugo J.B. Marroux

Dr Basile Curchod basile.f.curchod@durham.ac.uk
Academic Visitor

Charly A. Faradji

Timothy A. Shuttleworth

Hazel A. Sparkes

Paul G. Pringle

Andrew J. Orr-Ewing

Abstract

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 infrared 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.

Citation

Marroux, H. J., Curchod, B. F., Faradji, C. A., Shuttleworth, T. A., Sparkes, H. A., Pringle, P. G., & Orr-Ewing, A. J. (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

Journal Article Type	Article
Acceptance Date	Sep 4, 2017
Online Publication Date	Sep 22, 2017
Publication Date	Oct 23, 2017
Deposit Date	Nov 6, 2017
Publicly Available Date	Sep 22, 2018
Journal	Angewandte Chemie International Edition
Print ISSN	1433-7851
Electronic ISSN	1521-3773
Publisher	Wiley
Peer Reviewed	Peer Reviewed
Volume	56
Issue	44
Pages	13713-13716
DOI	https://doi.org/10.1002/anie.201707508
Related Public URLs	https://research-information.bristol.ac.uk/en/publications/spin-changes-accompany-ultrafast-structural-interconversion-in-the-ground-state-of-a-cobalt-nitrosyl-complex(781062a0-e546-4f7b-90bd-b747c8bb32d9).html

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Copyright Statement
This is the peer reviewed version of the following article: Marroux, Hugo J. B., Curchod, Basile F. E., Faradji, Charly A., Shuttleworth, Timothy A., Sparkes, Hazel A., Pringle, Paul G. & Orr-Ewing, Andrew J. (2017). Spin Changes Accompany Ultrafast Structural Interconversion in the Ground State of a Cobalt Nitrosyl Complex. Angewandte Chemie International Edition 56(44): 13713-13716, which has been published in final form at https://doi.org/10.1002/anie.201707508. This article may be used for non-commercial purposes in accordance With Wiley-VCH Terms and Conditions for self-archiving.