Elucidation of the photoaquation reaction mechanism in ferrous hexacyanide using synchrotron x-rays with sub-pulse-duration sensitivity

Anne Marie March, Gilles Doumy, Amity Andersen, Andre Al Haddad, Yoshiaki Kumagai, Ming Feng Tu, Joohee Bang, Christoph Bostedt, Jens Uhlig, Daniel R. Nascimento, Tadesse A. Assefa, Zoltán Németh, György Vankó, Wojciech Gawelda, Niranjan Govind, Linda Young

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Ligand substitution reactions are common in solvated transition metal complexes, and harnessing them through initiation with light promises interesting practical applications, driving interest in new means of probing their mechanisms. Using a combination of time-resolved x-ray absorption spectroscopy and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations and x-ray absorption near-edge spectroscopy calculations, we elucidate the mechanism of photoaquation in the model system iron(ii) hexacyanide, where UV excitation results in the exchange of a CN- ligand with a water molecule from the solvent. We take advantage of the high flux and stability of synchrotron x-rays to capture high precision x-ray absorption spectra that allow us to overcome the usual limitation of the relatively long x-ray pulses and extract the spectrum of the short-lived intermediate pentacoordinated species. Additionally, we determine its lifetime to be 19 (±5) ps. The QM/MM simulations support our experimental findings and explain the ∼20 ps time scale for aquation as involving interconversion between the square pyramidal (SP) and trigonal bipyramidal pentacoordinated geometries, with aquation being only active in the SP configuration.

Original languageEnglish
Article number144306
JournalJournal of Chemical Physics
Volume151
Issue number14
DOIs
Publication statusPublished - Oct 14 2019

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Synchrotrons
x ray absorption
synchrotrons
pulse duration
X rays
quantum mechanics
sensitivity
Molecular mechanics
Quantum theory
ligands
x rays
x ray spectra
x ray spectroscopy
absorption spectroscopy
Ligands
simulation
transition metals
substitutes
molecular dynamics
Coordination Complexes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Elucidation of the photoaquation reaction mechanism in ferrous hexacyanide using synchrotron x-rays with sub-pulse-duration sensitivity. / March, Anne Marie; Doumy, Gilles; Andersen, Amity; Al Haddad, Andre; Kumagai, Yoshiaki; Tu, Ming Feng; Bang, Joohee; Bostedt, Christoph; Uhlig, Jens; Nascimento, Daniel R.; Assefa, Tadesse A.; Németh, Zoltán; Vankó, György; Gawelda, Wojciech; Govind, Niranjan; Young, Linda.

In: Journal of Chemical Physics, Vol. 151, No. 14, 144306, 14.10.2019.

Research output: Contribution to journalArticle

March, AM, Doumy, G, Andersen, A, Al Haddad, A, Kumagai, Y, Tu, MF, Bang, J, Bostedt, C, Uhlig, J, Nascimento, DR, Assefa, TA, Németh, Z, Vankó, G, Gawelda, W, Govind, N & Young, L 2019, 'Elucidation of the photoaquation reaction mechanism in ferrous hexacyanide using synchrotron x-rays with sub-pulse-duration sensitivity', Journal of Chemical Physics, vol. 151, no. 14, 144306. https://doi.org/10.1063/1.5117318
March, Anne Marie ; Doumy, Gilles ; Andersen, Amity ; Al Haddad, Andre ; Kumagai, Yoshiaki ; Tu, Ming Feng ; Bang, Joohee ; Bostedt, Christoph ; Uhlig, Jens ; Nascimento, Daniel R. ; Assefa, Tadesse A. ; Németh, Zoltán ; Vankó, György ; Gawelda, Wojciech ; Govind, Niranjan ; Young, Linda. / Elucidation of the photoaquation reaction mechanism in ferrous hexacyanide using synchrotron x-rays with sub-pulse-duration sensitivity. In: Journal of Chemical Physics. 2019 ; Vol. 151, No. 14.
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