Photoaquation mechanism of hexacyanoferrate(II) ions: ultrafast 2D UV and transient visible and IR spectroscopies

Reinhard, Marco; Aub�ck, Gerald; Besley, Nicholas A.; Clark, Ian P.; Greetham, Gregory M.; Hanson-Heine, Magnus W.D.; Horvath, Raphael; Murphy, Thomas S.; Penfold, Thomas J.; Towrie, Michael; George, Michael W.; Chergui, Majed

Abstract

Ferrous iron(II) hexacyanide in aqueous solutions is known to undergo photoionization and photoaquation reactions depending on the excitation wavelength. To investigate this wavelength dependence, we implemented ultrafast two-dimensional UV transient absorption spectroscopy, covering a range from 280 to 370 nm in both excitation and probing, along with UV pump/visible probe or time-resolved infrared (TRIR) transient absorption spectroscopy and density functional theory (DFT) calculations. As far as photoaquation is concerned, we find that excitation of the molecule leads to ultrafast intramolecular relaxation to the lowest triplet state of the [Fe(CN)6]4– complex, followed by its dissociation into CN– and [Fe(CN)5]3– fragments and partial geminate recombination, all within

Citation

Reinhard, M., Auböck, G., Besley, N. A., Clark, I. P., Greetham, G. M., Hanson-Heine, M. W., …Chergui, M. (2017). Photoaquation mechanism of hexacyanoferrate(II) ions: ultrafast 2D UV and transient visible and IR spectroscopies. Journal of the American Chemical Society, 139(21), 7335-7347. https://doi.org/10.1021/jacs.7b02769

• Journal Article Type: Article
• Acceptance Date: Mar 6, 2017
• Online Publication Date: May 9, 2017
• Publication Date: May 31, 2017
• Deposit Date: May 26, 2017
• Publicly Available Date: May 26, 2017
• Journal: Journal of the American Chemical Society
• Print ISSN: 0002-7863
• Electronic ISSN: 1520-5126
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 139
• Issue: 21
• Pages: 7335-7347
• DOI: https://doi.org/10.1021/jacs.7b02769
• Public URL: https://nottingham-repository.worktribe.com/output/860070
• Publisher URL: http://pubs.acs.org/doi/abs/10.1021/jacs.7b02769
• Additional Information: This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Journal of the American Chemical Society, copyright © American Chemical Society after peer review. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.7b02769