Linkage Photoisomerization of an Isolated Ruthenium Sulfoxide Complex:Sequential versus Concerted Rearrangement

Scholz, Michael S., Bull, James N., 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

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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
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Depositing User: LivePure Connector
Date Deposited: 28 Feb 2019 16:30
Last Modified: 25 Jul 2019 02:04
URI: https://ueaeprints.uea.ac.uk/id/eprint/70054
DOI: 10.1021/acs.inorgchem.8b00871

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