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.
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21 August 2019
Research Article|
August 19 2019
Resonant inelastic X-ray scattering of a Ru photosensitizer: Insights from individual ligands to the electronic structure of the complete molecule
Robert H. Temperton
;
Robert H. Temperton
1
School of Physics and Astronomy, University of Nottingham
, Nottingham, NG7 2RD, United Kingdom
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Stephen T. Skowron
;
Stephen T. Skowron
2
School of Chemistry, University of Nottingham
, Nottingham, NG7 2RD, United Kingdom
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Karsten Handrup;
Karsten Handrup
3
Synchrotron Radiation Research, Department of Physics
, Box 118, SE-221 00 Lund, Sweden
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Andrew J. Gibson
;
Andrew J. Gibson
1
School of Physics and Astronomy, University of Nottingham
, Nottingham, NG7 2RD, United Kingdom
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Alessandro Nicolaou;
Alessandro Nicolaou
4
Synchrotron SOLEIL
, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette, France
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Nicolas Jaouen
;
Nicolas Jaouen
4
Synchrotron SOLEIL
, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette, France
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Elena Besley
;
Elena Besley
2
School of Chemistry, University of Nottingham
, Nottingham, NG7 2RD, United Kingdom
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James N. O’Shea
James N. O’Shea
a)
1
School of Physics and Astronomy, University of Nottingham
, Nottingham, NG7 2RD, United Kingdom
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Robert H. Temperton
1
Stephen T. Skowron
2
Karsten Handrup
3
Andrew J. Gibson
1
Alessandro Nicolaou
4
Nicolas Jaouen
4
Elena Besley
2
James N. O’Shea
1,a)
1
School of Physics and Astronomy, University of Nottingham
, Nottingham, NG7 2RD, United Kingdom
2
School of Chemistry, University of Nottingham
, Nottingham, NG7 2RD, United Kingdom
3
Synchrotron Radiation Research, Department of Physics
, Box 118, SE-221 00 Lund, Sweden
4
Synchrotron SOLEIL
, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette, France
a)
Electronic mail: [email protected]
J. Chem. Phys. 151, 074701 (2019)
Article history
Received:
June 11 2019
Accepted:
July 25 2019
Citation
Robert H. Temperton, Stephen T. Skowron, Karsten Handrup, Andrew J. Gibson, Alessandro Nicolaou, Nicolas Jaouen, Elena Besley, James N. O’Shea; Resonant inelastic X-ray scattering of a Ru photosensitizer: Insights from individual ligands to the electronic structure of the complete molecule. J. Chem. Phys. 21 August 2019; 151 (7): 074701. https://doi.org/10.1063/1.5114692
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