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Spin changes accompany ultrafast structural interconversion in the ground state of a cobalt nitrosyl complex

Research output: Contribution to journalArticle

Original languageEnglish
JournalAngewandte Chemie International Edition
Early online date4 Sep 2017
DOIs
StateE-pub ahead of print - 4 Sep 2017

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 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.

    Research areas

  • INTERSYSTEM CROSSING, ULTRAFAST DYNAMICS, 2DIR, ELECTRON SPIN, EXCHANGE

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  • Full-text PDF (accepted author manuscript)

    Rights statement: This is the author accepted manuscript (AAM). The final published version (version of record) is available online via Wiley at http://onlinelibrary.wiley.com/doi/10.1002/anie.201707508/abstract. Please refer to any applicable terms of use of the publisher.

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