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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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 languageEnglish
Article number13678
JournalNature Communications
Number of pages35
Publication statusPublished - 2016

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  • Excited states
  • Photocatalysis


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