Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts

S.E. Canton; X.Y. Zhang; J.X. Zhang; Tim Brandt van Driel; Kasper Skov Kjær; Martin Kristoffer Haldrup; P. Chabera; T. Harlang; K. Suarez-Alcantara; Y.Z. Liu; Morten Christensen; Henrik Till Lemke; Klaus Braagaard Møller; Martin Meedom Nielsen

doi:10.1021/jz401016h

Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts

S.E. Canton, X.Y. Zhang, J.X. Zhang, Tim Brandt van Driel, Kasper Skov Kjær, Martin Kristoffer Haldrup, P. Chabera, T. Harlang, K. Suarez-Alcantara, Y.Z. Liu, Morten Christensen, Henrik Till Lemke, Klaus Braagaard Møller, Martin Meedom Nielsen

Condensed Matter Physics

46 Citations (Scopus)

Abstract

Building a detailed understanding of the structure-function relationship is a crucial step in the optimization of molecular photocatalysts employed in water splitting schemes. The optically dark nature of their active sites usually prevents a complete mapping of the photoinduced dynamics. In this work, transient X-ray absorption spectroscopy highlights the electronic and geometric changes that affect such a center in a bimetallic model complex. Upon selective excitation of the ruthenium chromophore, the cobalt moiety is reduced through intramolecular electron transfer and undergoes a spin flip accompanied by an average bond elongation of 0.20 ± 0.03 Å. The analysis is supported by simulations based on density functional theory structures (B3LYP*/TZVP) and FEFF 9.0 multiple scattering calculations. More generally, these results exemplify the large potential of the technique for tracking elusive intermediates that impart unique functionalities in photochemical devices.

Original language	English
Journal	Journal of Physical Chemistry Letters
Volume	4
Issue number	11
Pages (from-to)	1972-1976
ISSN	1948-7185
DOIs	https://doi.org/10.1021/jz401016h
Publication status	Published - 6 Jun 2013

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Canton, S. E., Zhang, X. Y., Zhang, J. X., Brandt van Driel, T., Kjær, K. S., Haldrup, M. K., Chabera, P., Harlang, T., Suarez-Alcantara, K., Liu, Y. Z., Christensen, M., Lemke, H. T., Møller, K. B., & Nielsen, M. M. (2013). Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts. Journal of Physical Chemistry Letters, 4(11), 1972-1976. https://doi.org/10.1021/jz401016h

Canton, SE, Zhang, XY, Zhang, JX, Brandt van Driel, T, Kjær, KS, Haldrup, MK, Chabera, P, Harlang, T, Suarez-Alcantara, K, Liu, YZ, Christensen, M, Lemke, HT, Møller, KB & Nielsen, MM 2013, 'Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts', Journal of Physical Chemistry Letters, vol. 4, no. 11, pp. 1972-1976. https://doi.org/10.1021/jz401016h

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abstract = "Building a detailed understanding of the structure-function relationship is a crucial step in the optimization of molecular photocatalysts employed in water splitting schemes. The optically dark nature of their active sites usually prevents a complete mapping of the photoinduced dynamics. In this work, transient X-ray absorption spectroscopy highlights the electronic and geometric changes that affect such a center in a bimetallic model complex. Upon selective excitation of the ruthenium chromophore, the cobalt moiety is reduced through intramolecular electron transfer and undergoes a spin flip accompanied by an average bond elongation of 0.20 ± 0.03 {\AA}. The analysis is supported by simulations based on density functional theory structures (B3LYP*/TZVP) and FEFF 9.0 multiple scattering calculations. More generally, these results exemplify the large potential of the technique for tracking elusive intermediates that impart unique functionalities in photochemical devices.",

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AU - Canton, S.E.

AU - Zhang, X.Y.

AU - Zhang, J.X.

AU - Brandt van Driel, Tim

AU - Kjær, Kasper Skov

AU - Haldrup, Martin Kristoffer

AU - Chabera, P.

AU - Harlang, T.

AU - Suarez-Alcantara, K.

AU - Liu, Y.Z.

AU - Christensen, Morten

AU - Lemke, Henrik Till

AU - Møller, Klaus Braagaard

AU - Nielsen, Martin Meedom

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N2 - Building a detailed understanding of the structure-function relationship is a crucial step in the optimization of molecular photocatalysts employed in water splitting schemes. The optically dark nature of their active sites usually prevents a complete mapping of the photoinduced dynamics. In this work, transient X-ray absorption spectroscopy highlights the electronic and geometric changes that affect such a center in a bimetallic model complex. Upon selective excitation of the ruthenium chromophore, the cobalt moiety is reduced through intramolecular electron transfer and undergoes a spin flip accompanied by an average bond elongation of 0.20 ± 0.03 Å. The analysis is supported by simulations based on density functional theory structures (B3LYP*/TZVP) and FEFF 9.0 multiple scattering calculations. More generally, these results exemplify the large potential of the technique for tracking elusive intermediates that impart unique functionalities in photochemical devices.

AB - Building a detailed understanding of the structure-function relationship is a crucial step in the optimization of molecular photocatalysts employed in water splitting schemes. The optically dark nature of their active sites usually prevents a complete mapping of the photoinduced dynamics. In this work, transient X-ray absorption spectroscopy highlights the electronic and geometric changes that affect such a center in a bimetallic model complex. Upon selective excitation of the ruthenium chromophore, the cobalt moiety is reduced through intramolecular electron transfer and undergoes a spin flip accompanied by an average bond elongation of 0.20 ± 0.03 Å. The analysis is supported by simulations based on density functional theory structures (B3LYP*/TZVP) and FEFF 9.0 multiple scattering calculations. More generally, these results exemplify the large potential of the technique for tracking elusive intermediates that impart unique functionalities in photochemical devices.

U2 - 10.1021/jz401016h

DO - 10.1021/jz401016h

M3 - Journal article

SN - 1948-7185

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SP - 1972

EP - 1976

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

IS - 11

ER -

Toward Highlighting the Ultrafast Electron Transfer Dynamics at the Optically Dark Sites of Photocatalysts

Abstract

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