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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 LU ; Gibson, Andrew J.; Nicolaou, Alessandro; Jaouen, Nicolas; Besley, Elena and O'Shea, James N. (2019) In Journal of Chemical Physics 151(7).
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... (More)

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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author
organization
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Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
151
issue
7
publisher
American Institute of Physics
external identifiers
  • scopus:85071273368
ISSN
0021-9606
DOI
10.1063/1.5114692
language
English
LU publication?
yes
id
97aba39b-1a15-444e-a6a8-bc97615da2d5
date added to LUP
2019-09-09 15:14:30
date last changed
2019-10-01 03:46:58
@article{97aba39b-1a15-444e-a6a8-bc97615da2d5,
  abstract     = {<p>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.</p>},
  articleno    = {074701},
  author       = {Temperton, Robert H. and Skowron, Stephen T. and Handrup, Karsten and Gibson, Andrew J. and Nicolaou, Alessandro and Jaouen, Nicolas and Besley, Elena and O'Shea, James N.},
  issn         = {0021-9606},
  language     = {eng},
  month        = {08},
  number       = {7},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Resonant inelastic X-ray scattering of a Ru photosensitizer : Insights from individual ligands to the electronic structure of the complete molecule},
  url          = {http://dx.doi.org/10.1063/1.5114692},
  volume       = {151},
  year         = {2019},
}