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

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2023 Oct 19

PMID 37856865

Authors

Yunbeom Lee

Hosung Ki

Donghwan Im

Seunghwan Eom

Jain Gu

Seonggon Lee

Jungmin Kim

Yongjun Cha

Kyung Won Lee

Serhane Zerdane

Matteo Levantino

Hyotcherl Ihee

Affiliations

Soon will be listed here.

Abstract

[Ce(III)Cl], 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]. Structural analysis of the TRXL data revealed that the excited state of [Ce(III)Cl] 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.

References

Choi E, Kim J, Kim J, Ki H, Lee Y, Lee S . Filming ultrafast roaming-mediated isomerization of bismuth triiodide in solution. Nat Commun. 2021; 12(1):4732. PMC: 8342516. DOI: 10.1038/s41467-021-25070-z. View

Leshchev D, Valentine A, Kim P, Mills A, Roy S, Chakraborty A . Revealing Excited-State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time. Angew Chem Int Ed Engl. 2023; 62(28):e202304615. DOI: 10.1002/anie.202304615. View

van Driel T, Kjaer K, Hartsock R, Dohn A, Harlang T, Chollet M . Atomistic characterization of the active-site solvation dynamics of a model photocatalyst. Nat Commun. 2016; 7:13678. PMC: 5133712. DOI: 10.1038/ncomms13678. View

Guo J, Hu A, Chen Y, Sun J, Tang H, Zuo Z . Photocatalytic C-C Bond Cleavage and Amination of Cycloalkanols by Cerium(III) Chloride Complex. Angew Chem Int Ed Engl. 2016; 55(49):15319-15322. DOI: 10.1002/anie.201609035. View

Ki H, Kim T, Moon J, Kim J, Lee Y, Heo J . Photoactivation of triosmium dodecacarbonyl at 400 nm probed with time-resolved X-ray liquidography. Chem Commun (Camb). 2022; 58(53):7380-7383. DOI: 10.1039/d2cc02438a. View

Tanner P, Mak C, Edelstein N, Murdoch K, Liu G, Huang J . Absorption and emission spectra of Ce3+ in elpasolite lattices. J Am Chem Soc. 2003; 125(43):13225-33. DOI: 10.1021/ja036659x. View

Kim T, Lorenc M, Lee J, Lo Russo M, Kim J, Cammarata M . Spatiotemporal reaction kinetics of an ultrafast photoreaction pathway visualized by time-resolved liquid x-ray diffraction. Proc Natl Acad Sci U S A. 2006; 103(25):9410-5. PMC: 1478163. DOI: 10.1073/pnas.0601958103. View

Kim J, Nozawa S, Kim H, Choi E, Sato T, Kim T . Mapping the emergence of molecular vibrations mediating bond formation. Nature. 2020; 582(7813):520-524. DOI: 10.1038/s41586-020-2417-3. View

Yin H, Jin Y, Hertzog J, Mullane K, Carroll P, Manor B . The Hexachlorocerate(III) Anion: A Potent, Benchtop Stable, and Readily Available Ultraviolet A Photosensitizer for Aryl Chlorides. J Am Chem Soc. 2016; 138(50):16266-16273. DOI: 10.1021/jacs.6b05712. View

10.

Rimmerman D, Leshchev D, Hsu D, Hong J, Kosheleva I, Chen L . Direct Observation of Insulin Association Dynamics with Time-Resolved X-ray Scattering. J Phys Chem Lett. 2017; 8(18):4413-4418. PMC: 5804350. DOI: 10.1021/acs.jpclett.7b01720. View

11.

Schwarz J, Konig B . Visible-light mediated C-C bond cleavage of 1,2-diols to carbonyls by cerium-photocatalysis. Chem Commun (Camb). 2018; 55(4):486-488. DOI: 10.1039/c8cc09208g. View

12.

Lee Y, Kim J, Lee S, Muniyappan S, Kim T, Ki H . Ultrafast coherent motion and helix rearrangement of homodimeric hemoglobin visualized with femtosecond X-ray solution scattering. Nat Commun. 2021; 12(1):3677. PMC: 8209046. DOI: 10.1038/s41467-021-23947-7. View

13.

Kjaer K, van Driel T, Harlang T, Kunnus K, Biasin E, Ledbetter K . Finding intersections between electronic excited state potential energy surfaces with simultaneous ultrafast X-ray scattering and spectroscopy. Chem Sci. 2019; 10(22):5749-5760. PMC: 6568243. DOI: 10.1039/c8sc04023k. View

14.

Yin H, Carroll P, Manor B, Anna J, Schelter E . Cerium Photosensitizers: Structure-Function Relationships and Applications in Photocatalytic Aryl Coupling Reactions. J Am Chem Soc. 2016; 138(18):5984-93. DOI: 10.1021/jacs.6b02248. View

15.

Yin H, Carroll P, Anna J, Schelter E . Luminescent Ce(III) Complexes as Stoichiometric and Catalytic Photoreductants for Halogen Atom Abstraction Reactions. J Am Chem Soc. 2015; 137(29):9234-7. DOI: 10.1021/jacs.5b05411. View

16.

Treacy S, Rovis T . Copper Catalyzed C(sp)-H Bond Alkylation via Photoinduced Ligand-to-Metal Charge Transfer. J Am Chem Soc. 2021; 143(7):2729-2735. PMC: 8608032. DOI: 10.1021/jacs.1c00687. View

17.

Park Y, Kim Y, Chang S . Transition Metal-Catalyzed C-H Amination: Scope, Mechanism, and Applications. Chem Rev. 2017; 117(13):9247-9301. DOI: 10.1021/acs.chemrev.6b00644. View

18.

Mkhalid I, Barnard J, Marder T, Murphy J, Hartwig J . C-H activation for the construction of C-B bonds. Chem Rev. 2009; 110(2):890-931. DOI: 10.1021/cr900206p. View

19.

An Q, Wang Z, Chen Y, Wang X, Zhang K, Pan H . Cerium-Catalyzed C-H Functionalizations of Alkanes Utilizing Alcohols as Hydrogen Atom Transfer Agents. J Am Chem Soc. 2020; 142(13):6216-6226. DOI: 10.1021/jacs.0c00212. View

20.

Hu A, Guo J, Pan H, Zuo Z . Selective functionalization of methane, ethane, and higher alkanes by cerium photocatalysis. Science. 2018; 361(6403):668-672. DOI: 10.1126/science.aat9750. View