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Scholz, Michael S., Bull, James N. 
ORCID: https://orcid.org/0000-0003-0953-1716, Carrascosa, Eduardo, Adamson, Brian D., Kosgei, Gilbert K., Rack, Jeffrey J. and Bieske, Evan J.
(2018)
Linkage photoisomerization of an isolated ruthenium sulfoxide complex: Sequential versus concerted rearrangement.
Inorganic Chemistry, 57 (9).
pp. 5701-5706.
ISSN 0020-1669
Abstract
Ruthenium sulfoxide complexes undergo thermally reversible linkage isomerization of sulfoxide ligands from S- to O-bound in response to light. Here, we report photoisomerization action spectra for a ruthenium bis-sulfoxide molecular photoswitch, [Ru(bpy)2(bpSO)]2+, providing the first direct evidence for photoisomerization of a transition metal complex in the gas phase. The linkage isomers are separated and isolated in a tandem drift tube ion mobility spectrometer and exposed to tunable laser radiation provoking photoisomerization. Direct switching of the S,S-isomer to the O,O-isomer following absorption of a single photon is the predominant isomerization pathway in the gas phase, unlike in solution, where stepwise isomerization is observed with each sulfoxide ligand switching in turn. The change in isomerization dynamics is attributed to rapid vibrational quenching that suppresses isomerization in solution. Supporting electronic structure calculations predict the wavelengths and intensities of the peaks in the photoisomerization action spectra of the S,S- and S,O-isomers, indicating that they correspond to metal-to-ligand charge transfer (MLCT) and ligand-centered ππ∗ transitions.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | physical and theoretical chemistry,inorganic chemistry ,/dk/atira/pure/subjectarea/asjc/1600/1606 |
| Faculty \ School: | Faculty of Science > School of Chemistry (former - to 2024) |
| UEA Research Groups: | Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Centre for Photonics and Quantum Science |
| Related URLs: | |
| Depositing User: | LivePure Connector |
| Date Deposited: | 28 Feb 2019 16:30 |
| Last Modified: | 25 Sep 2024 13:54 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/70054 |
| DOI: | 10.1021/acs.inorgchem.8b00871 |
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