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Issue 22, 2020
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An excited state dynamics driven reaction: wavelength-dependent photoisomerization quantum yields in [Ru(bpy)2(dmso)2]2+

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Abstract

We report the excited-state behavior of a structurally simple bis-sulfoxide complex, cis-S,S-[Ru(bpy)2(dmso)2]2+, as investigated by femtosecond pump–probe spectroscopy. The results reveal that a single photon prompts phototriggered isomerization of one or both dmso ligands to yield a mixture of cis-S,O-[Ru(bpy)2(dmso)2]2+ and cis-O,O-[Ru(bpy)2(dmso)2]2+. The quantum yields of isomerization of each product and relative product distribution are dependent upon the excitation wavelength, with longer wavelengths favoring the double isomerization product, cis-O,O-[Ru(bpy)2(dmso)2]2+. Transient absorption measurements on cis-O,O-[Ru(bpy)2(dmso)2]2+ do not reveal an excited-state isomerization pathway to produce either the S,O or S,S isomers. Femtosecond pulse shaping experiments reveal no change in the product distribution. Pump–repump–probe transient absorption spectroscopy of cis-S,S-[Ru(bpy)2(dmso)2]2+ shows that a pump–repump time delay of 3 ps dramatically alters the S,O : O,O product ratio; pump–repump–probe transient absorption spectroscopy of cis-O,O-[Ru(bpy)2(dmso)2]2+ with a time delay of 3 ps uncovers an excited-state isomerization pathway to produce the S,O isomer. In conjunction with low-temperature steady-state emission spectroscopy, these results are interpreted in the context of an excited-state bifurcating pathway, in which the isomerization product distribution is determined not by thermodynamics, but rather as a dynamics driven reaction.

Graphical abstract: An excited state dynamics driven reaction: wavelength-dependent photoisomerization quantum yields in [Ru(bpy)2(dmso)2]2+

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Supplementary files

Article information


Submitted
29 Jan 2020
Accepted
17 May 2020
First published
27 May 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 5797-5807
Article type
Edge Article

An excited state dynamics driven reaction: wavelength-dependent photoisomerization quantum yields in [Ru(bpy)2(dmso)2]2+

M. Y. Livshits, L. Wang, S. B. Vittardi, S. Ruetzel, A. King, T. Brixner and J. J. Rack, Chem. Sci., 2020, 11, 5797
DOI: 10.1039/D0SC00551G

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