Atomistic characterization of the active-site solvation dynamics of a model photocatalyst

Tim Brandt van Driel; Kasper Skov Kjær; Robert W. Hartsock; Asmus Ougaard Dohn; Tobias C. B. Harlang; Matthieu Chollet; Morten Christensen; Wojciech Gawelda; Niels Engholm Henriksen; Kristoffer Haldrup; Kyung Hwan Kim; Hyotcherl Ihee; Jeongho Kim; Henrik Till Lemke; Zheng Sun; Villy Sundström; Wenkai Zhang; Diling Zhu; Klaus Braagaard Møller; Martin Meedom Nielsen; Kelly J. Gaffney

doi:10.1038/ncomms13678

Atomistic characterization of the active-site solvation dynamics of a model photocatalyst

Tim Brandt van Driel, Kasper Skov Kjær, Robert W. Hartsock, Asmus Ougaard Dohn, Tobias C. B. Harlang, Matthieu Chollet, Morten Christensen, Wojciech Gawelda, Niels Engholm Henriksen, Kristoffer Haldrup, Kyung Hwan Kim, Hyotcherl Ihee, Jeongho Kim, Henrik Till Lemke, Zheng Sun, Villy Sundström, Wenkai Zhang, Diling Zhu, Klaus Braagaard Møller, Martin Meedom NielsenKelly J. Gaffney

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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 [Ir₂(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.

Original language	English
Article number	13678
Journal	Nature Communications
Volume	7
Number of pages	35
ISSN	2041-1723
DOIs	https://doi.org/10.1038/ncomms13678
Publication status	Published - 2016

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This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

Keywords

Excited states
Photocatalysis

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Brandt van Driel, T., Kjær, K. S., Hartsock, R. W., Dohn, A. O., Harlang, T. C. B., Chollet, M., Christensen, M., Gawelda, W., Henriksen, N. E., Haldrup, K., Kim, K. H., Ihee, H., Kim, J., Lemke, H. T., Sun, Z., Sundström, V., Zhang, W., Zhu, D., Møller, K. B., ... Gaffney, K. J. (2016). Atomistic characterization of the active-site solvation dynamics of a model photocatalyst. Nature Communications, 7, Article 13678. https://doi.org/10.1038/ncomms13678

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title = "Atomistic characterization of the active-site solvation dynamics of a model photocatalyst",

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 [Ir2(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.",

keywords = "Excited states, Photocatalysis",

author = "{Brandt van Driel}, Tim and Kj{\ae}r, {Kasper Skov} and Hartsock, {Robert W.} and Dohn, {Asmus Ougaard} and Harlang, {Tobias C. B.} and Matthieu Chollet and Morten Christensen and Wojciech Gawelda and Henriksen, {Niels Engholm} and Kristoffer Haldrup and Kim, {Kyung Hwan} and Hyotcherl Ihee and Jeongho Kim and Lemke, {Henrik Till} and Zheng Sun and Villy Sundstr{\"o}m and Wenkai Zhang and Diling Zhu and M{\o}ller, {Klaus Braagaard} and Nielsen, {Martin Meedom} and Gaffney, {Kelly J.}",

note = "This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article{\textquoteright}s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ ",

year = "2016",

doi = "10.1038/ncomms13678",

language = "English",

volume = "7",

journal = "Nature Communications",

issn = "2041-1723",

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Brandt van Driel, T, Kjær, KS, Hartsock, RW, Dohn, AO, Harlang, TCB, Chollet, M, Christensen, M, Gawelda, W, Henriksen, NE , Haldrup, K, Kim, KH, Ihee, H, Kim, J, Lemke, HT, Sun, Z, Sundström, V, Zhang, W, Zhu, D, Møller, KB , Nielsen, MM & Gaffney, KJ 2016, 'Atomistic characterization of the active-site solvation dynamics of a model photocatalyst', Nature Communications, vol. 7, 13678. https://doi.org/10.1038/ncomms13678

TY - JOUR

T1 - Atomistic characterization of the active-site solvation dynamics of a model photocatalyst

AU - Brandt van Driel, Tim

AU - Kjær, Kasper Skov

AU - Hartsock, Robert W.

AU - Dohn, Asmus Ougaard

AU - Harlang, Tobias C. B.

AU - Chollet, Matthieu

AU - Christensen, Morten

AU - Gawelda, Wojciech

AU - Henriksen, Niels Engholm

AU - Haldrup, Kristoffer

AU - Kim, Kyung Hwan

AU - Ihee, Hyotcherl

AU - Kim, Jeongho

AU - Lemke, Henrik Till

AU - Sun, Zheng

AU - Sundström, Villy

AU - Zhang, Wenkai

AU - Zhu, Diling

AU - Møller, Klaus Braagaard

AU - Nielsen, Martin Meedom

AU - Gaffney, Kelly J.

N1 - This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

PY - 2016

Y1 - 2016

N2 - 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 [Ir2(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.

AB - 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 [Ir2(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.

KW - Excited states

KW - Photocatalysis

U2 - 10.1038/ncomms13678

DO - 10.1038/ncomms13678

M3 - Journal article

C2 - 27892472

SN - 2041-1723

VL - 7

JO - Nature Communications

JF - Nature Communications

M1 - 13678

ER -

Atomistic characterization of the active-site solvation dynamics of a model photocatalyst

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