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Resonant inelastic X-ray scattering of a Ru photosensitizer: Insights from individual ligands to the electronic structure of the complete molecule

Temperton, Robert H.; Skowron, Stephen T.; Handrup, Karsten; Gibson, Andrew J.; Nicolaou, Alessandro; Jaouen, Nicolas; Besley, Elena; O’Shea, James N.

Authors

Robert H. Temperton

Stephen T. Skowron

Karsten Handrup

Andrew J. Gibson

Alessandro Nicolaou

Nicolas Jaouen

Elena Besley

James N. O’Shea



Abstract

N 1s Resonant Inelastic X-ray Scattering (RIXS) was used to probe the molecular electronic structure of the ruthenium photosensitizer complex cis-bis(isothiocyanato) bis(2,2′-bipyridyl-4,4′-dicarboxylato) ruthenium(II), known as “N3.” In order to interpret these data, crystalline powder samples of the bipyridine-dicarboxylic acid ligand (“bi-isonicotinic acid”) and the single ring analog “isonicotinic acid” were studied separately using the same method. Clear evidence for intermolecular hydrogen bonding is observed for each of these crystalline powders, along with clear vibronic coupling features. For bi-isonicotinic acid, these results are compared to those of a physisorbed multilayer, where no hydrogen bonding is observed. The RIXS of the “N3” dye, again prepared as a bulk powder sample, is interpreted in terms of the orbital contributions of the bi-isonicotinic acid and thiocyanate ligands by considering the two different nitrogen species. This allows direct comparison with the isolated ligand molecules where we highlight the impact of the central Ru atom on the electronic structure of the ligand. Further interpretation is provided through complementary resonant photoemission spectroscopy and density functional theory calculations. This combination of techniques allows us to confirm the localization and relative coupling of the frontier orbitals and associated vibrational losses.

Journal Article Type Article
Publication Date Aug 21, 2019
Journal The Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher AIP Publishing
Peer Reviewed Peer Reviewed
Volume 151
Issue 7
Article Number 074701
Pages 1-9
APA6 Citation Temperton, R. H., Skowron, S. T., Handrup, K., Gibson, A. J., Nicolaou, A., Jaouen, N., …O’Shea, J. N. (2019). Resonant inelastic X-ray scattering of a Ru photosensitizer: Insights from individual ligands to the electronic structure of the complete molecule. Journal of Chemical Physics, 151(7), 1-9. https://doi.org/10.1063/1.5114692
DOI https://doi.org/10.1063/1.5114692
Keywords Physical and Theoretical Chemistry; General Physics and Astronomy
Publisher URL https://aip.scitation.org/doi/10.1063/1.5114692
Additional Information Published under license by AIP Publishing.

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