Atomistic characterization of the active-site solvation dynamics of a model photocatalyst
(2016) In Nature Communications 7.- Abstract
The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynamics following excitation of a model photocatalytic molecular system [Ir 2 (dimen) 4 ] 2+, where dimen is para-diisocyanomenthane. The time-dependent structural changes in this model photocatalyst, as well as the changes in the solvation shell structure, have been measured with ultrafast diffuse X-ray scattering and simulated with Born-Oppenheimer Molecular Dynamics. Both methods provide direct access to the solute-solvent pair distribution... (More)
The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynamics following excitation of a model photocatalytic molecular system [Ir 2 (dimen) 4 ] 2+, where dimen is para-diisocyanomenthane. The time-dependent structural changes in this model photocatalyst, as well as the changes in the solvation shell structure, have been measured with ultrafast diffuse X-ray scattering and simulated with Born-Oppenheimer Molecular Dynamics. Both methods provide direct access to the solute-solvent pair distribution function, enabling the solvation dynamics around the catalytically active iridium sites to be robustly characterized. Our results provide evidence for the coordination of the iridium atoms by the acetonitrile solvent and demonstrate the viability of using diffuse X-ray scattering at free-electron laser sources for studying the dynamics of photocatalysis.
(Less)
- author
- organization
- publishing date
- 2016-11-28
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Nature Communications
- volume
- 7
- article number
- 13678
- publisher
- Nature Publishing Group
- external identifiers
-
- scopus:85000843958
- pmid:27892472
- wos:000388643800001
- ISSN
- 2041-1723
- DOI
- 10.1038/ncomms13678
- language
- English
- LU publication?
- yes
- id
- d804707e-18c0-4613-84d3-c5084cd9e757
- date added to LUP
- 2016-12-19 12:18:21
- date last changed
- 2024-04-05 13:06:14
@article{d804707e-18c0-4613-84d3-c5084cd9e757,
abstract = {{<p>The interactions between the reactive excited state of molecular photocatalysts and surrounding solvent dictate reaction mechanisms and pathways, but are not readily accessible to conventional optical spectroscopic techniques. Here we report an investigation of the structural and solvation dynamics following excitation of a model photocatalytic molecular system [Ir 2 (dimen) 4 ] 2+, where dimen is para-diisocyanomenthane. The time-dependent structural changes in this model photocatalyst, as well as the changes in the solvation shell structure, have been measured with ultrafast diffuse X-ray scattering and simulated with Born-Oppenheimer Molecular Dynamics. Both methods provide direct access to the solute-solvent pair distribution function, enabling the solvation dynamics around the catalytically active iridium sites to be robustly characterized. Our results provide evidence for the coordination of the iridium atoms by the acetonitrile solvent and demonstrate the viability of using diffuse X-ray scattering at free-electron laser sources for studying the dynamics of photocatalysis.</p>}},
author = {{Van Driel, Tim B. and Kjaer, Kasper S. and Hartsock, Robert W. and Dohn, Asmus O. and Harlang, Tobias and Chollet, Matthieu and Christensen, Morten and Gawelda, Wojciech and Henriksen, Niels E. and Kim, Jong Goo and Haldrup, Kristoffer and Kim, Kyung Hwan and Ihee, Hyotcherl and Kim, Jeongho and Lemke, Henrik and Sun, Zheng and Sundström, Villy and Zhang, Wenkai and Zhu, Diling and MØller, Klaus B. and Nielsen, Martin M. and Gaffney, Kelly J.}},
issn = {{2041-1723}},
language = {{eng}},
month = {{11}},
publisher = {{Nature Publishing Group}},
series = {{Nature Communications}},
title = {{Atomistic characterization of the active-site solvation dynamics of a model photocatalyst}},
url = {{http://dx.doi.org/10.1038/ncomms13678}},
doi = {{10.1038/ncomms13678}},
volume = {{7}},
year = {{2016}},
}