Photoactivation of triosmium dodecacarbonyl at 400 nm probed with time-resolved X-ray liquidography

Ki, Hosung; Kim, Tae W.; Moon, Jiwon; Kim, Jungmin; Lee, Yunbeom; Heo, Jun Neoung; Kim, Kyung Hwan; Kong, Qingyu; Khakhulin, Dmitry; Newby, Gemma; Kim, Joonghan; Kim, Jeongho; Wulff, Michaël; Ihee, Hyotcherl

doi:10.1039/d2cc02438a

Cited by 4 publications

(1 citation statement)

References 32 publications

(67 reference statements)

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“…To address these challenges, we employed time-resolved X-ray liquidography (TRXL), a technique that directly provides information about the transient structure of molecules in the liquid solution phase. TRXL is a potent technique that combines the pump–probe scheme with X-ray scattering, enabling extraction of molecular structures of short-lived species in solution during chemical reactions from the change in the X-ray scattering signal over time. , Indeed, TRXL has been demonstrated as a powerful tool for investigating the structural dynamics of metal complexes, including metal photocatalysts. − However, prior to this work, TRXL has not been applied to a solution containing both a photocatalyst and its substrate; in essence, TRXL had not been used to study a photocatalyst “in action”. To fill this gap, in this study, we aim to exploit the advantages of TRXL to investigate the structural dynamics, including the structures of reaction intermediates, of a Ce-based photocatalyst with its substrate.…”

Section: Introductionmentioning

confidence: 99%

Cerium Photocatalyst in Action: Structural Dynamics in the Presence of Substrate Visualized via Time-Resolved X-ray Liquidography

Lee,

Ki,

et al. 2023

J. Am. Chem. Soc.

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Metrics & MoreArticle Recommendations * sı Supporting InformationABSTRACT: [Ce(III)Cl 6 ] 3− , with its earth-abundant metal element, is a promising photocatalyst facilitating carbon−halogen bond activation. Still, the structure of the reaction intermediate has yet to be explored. Here, we applied time-resolved X-ray liquidography (TRXL), which allows for direct observation of the structural details of reaction intermediates, to investigate the photocatalytic reaction of [Ce(III)Cl 6 ] 3− . Structural analysis of the TRXL data revealed that the excited state of [Ce(III)Cl 6 ] 3− has Ce−Cl bonds that are shorter than those of the ground state and that the Ce−Cl bond further contracts upon oxidation. In addition, this study represents the first application of TRXL to both photocatalyst-only and photocatalyst-and-substrate samples, providing insights into the substrate's influence on the photocatalyst's reaction dynamics. This study demonstrates the capability of TRXL in elucidating the reaction dynamics of photocatalysts under various conditions and highlights the importance of experimental determination of the structures of reaction intermediates to advance our understanding of photocatalytic mechanisms.

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Section: Introductionmentioning

confidence: 99%

Cerium Photocatalyst in Action: Structural Dynamics in the Presence of Substrate Visualized via Time-Resolved X-ray Liquidography

Lee,

Ki,

et al. 2023

J. Am. Chem. Soc.

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The complex systems and biomedical sciences group at the ESRF: Current status and new opportunities after extremely brilliant source upgrade

Jankowski

Belova

Chushkin

et al. 2023

Nuclear Instruments and Methods in Physics Research Section B:

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Serial X-ray liquidography: multi-dimensional assay framework for exploring biomolecular structural dynamics with microgram quantities

Kim,

Yun,

Lee

et al. 2024

Nat Commun

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Understanding protein structure and kinetics under physiological conditions is crucial for elucidating complex biological processes. While time-resolved (TR) techniques have advanced to track molecular actions, their practical application in biological reactions is often confined to reversible photoreactions within limited experimental parameters due to inefficient sample utilization and inflexibility of experimental setups. Here, we introduce serial X-ray liquidography (SXL), a technique that combines time-resolved X-ray liquidography with a fixed target of serially arranged microchambers. SXL breaks through the previously mentioned barriers, enabling microgram-scale TR studies of both irreversible and reversible reactions of even a non-photoactive protein. We demonstrate its versatility in studying a wide range of biological reactions, highlighting its potential as a flexible and multi-dimensional assay framework for kinetic and structural characterization. Leveraging X-ray free-electron lasers and micro-focused X-ray pulses promises further enhancements in both temporal resolution and minimizing sample quantity. SXL offers unprecedented insights into the structural and kinetic landscapes of molecular actions, paving the way for a deeper understanding of complex biological processes.

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Photoactivation of triosmium dodecacarbonyl at 400 nm probed with time-resolved X-ray liquidography

Abstract: The photoactivation mechanism of Os3(CO)12 at 400 nm is examined with time-resolved X-ray liquidography. The data reveal two pathways: the vibrational relaxation following an internal conversion to the electronic ground...

Cited by 4 publications

References 32 publications

Cerium Photocatalyst in Action: Structural Dynamics in the Presence of Substrate Visualized via Time-Resolved X-ray Liquidography

Cerium Photocatalyst in Action: Structural Dynamics in the Presence of Substrate Visualized via Time-Resolved X-ray Liquidography

The complex systems and biomedical sciences group at the ESRF: Current status and new opportunities after extremely brilliant source upgrade

Serial X-ray liquidography: multi-dimensional assay framework for exploring biomolecular structural dynamics with microgram quantities

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