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.

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.

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

• Journal Article Type: Article
• Acceptance Date: Jul 25, 2019
• Online Publication Date: Aug 19, 2019
• Publication Date: Aug 21, 2019
• Deposit Date: Sep 17, 2019
• Publicly Available Date: Sep 18, 2019
• Journal: The Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 151
• Issue: 7
• Article Number: 074701
• Pages: 1-9
• DOI: https://doi.org/10.1063/1.5114692
• Keywords: Physical and Theoretical Chemistry; General Physics and Astronomy
• Public URL: https://nottingham-repository.worktribe.com/output/2470119
• Publisher URL: https://aip.scitation.org/doi/10.1063/1.5114692
• Additional Information: Published under license by AIP Publishing.