ArticleNature communications2023
Ferricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy.
Article in Nature communications, 2023. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 9 papers.
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Who cites it
9 citing papers in PubMed.
- Pursuing Heteroleptic Ligand Design Principles for Photoactive Fe Complexes with Ultrafast X-ray Emission and Variable-Temperature Optical Spectroscopies.Journal of the American Chemical Society · 2026Article
- Reversible single crystal photochemistry and spin state switching in a metal-cyanide complex.Nature communications · 2025Article
- Combined X-Ray Emission Spectroscopy at Phosphorus and Nickel: Detecting Subtle Changes in Catalyst Electronic Structure at High Resolution.Small (Weinheim an der Bergstrasse, Germany) · 2025Article
- Five-analyzer Johann spectrometer for hard X-ray photon-in/photon-out spectroscopy at the Inner Shell Spectroscopy beamline at NSLS-II: design, alignment and data acquisition.Journal of synchrotron radiation · 2024Article
- The Liquid Jet Endstation for Hard X-ray Scattering and Spectroscopy at the Linac Coherent Light Source.Molecules (Basel, Switzerland) · 2024Article
- Tailoring the Photophysical Properties of a Homoleptic Iron(II) TetraInorganic chemistry · 2024Article
- Experimental capabilities for liquid jet samples at sub-MHz rates at the FXE Instrument at European XFEL.Journal of synchrotron radiation · 2023Article
- Solution phase high repetition rate laser pump x-ray probe picosecond hard x-ray spectroscopy at the Stanford Synchrotron Radiation Lightsource.Structural dynamics (Melville, N.Y.) · 2023Article
- Ultrafast Optical Pump-Hard X-Ray Probe Spectroscopy of Transition Metal Complexes in Solution at SLAC.Synchrotron radiation newsArticle
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Authors and funding
18 authors.
Funding
Abstract
Reliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kβ main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kβ main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.
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