Accessing Photoredox Transformations with an Iron(III) Photosensitizer and Green Light
(2021) Journal of the American chemical society — Vol. 143, n° 38, p. 15661-15673 (2021)
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- Authors
Cadranel, Alejandro 
- Abstract
- Efficient excited-state electron transfer between an iron(III) photosensitizer and organic electron donors was realized with green light irradiation. This advance was enabled by the use of the previously reported iron photosensitizer, [Fe(phtmeimb)2]+ (phtmeimb = {phenyl[tris(3-methyl-imidazolin-2-ylidene)]borate}, that exhibited long-lived and luminescent ligand-to-metal charge-transfer (LMCT) excited states. A benchmark dehalogenation reaction was investigated with yields that exceed 90% and an enhanced stability relative to the prototypical photosensitizer [Ru(bpy)3]2+. The initial catalytic step is electron transfer from an amine to the photoexcited iron sensitizer, which is shown to occur with a large cage-escape yield. For LMCT excited states, this reductive electron transfer is vectorial and may be a general advantage of Fe(III) photosensitizers. In-depth time-resolved spectroscopic methods, including transient absorption characterization from the ultraviolet to the infrared regions, provided a quantitative description of the catalytic mechanism with associated rate constants and yields.
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Citations
Aydogan, A., Bangle, R. E., Cadranel, A., Turlington, M. D., Conroy, D. T., Cauët, E., Singleton, M., Meyer, G. J., Sampaio, R. N., Elias, B., & Troian-Gautier, L. (2021). Accessing Photoredox Transformations with an Iron(III) Photosensitizer and Green Light. Journal of the American chemical society, 143(38), 15661-15673. https://doi.org/10.1021/jacs.1c06081 (Original work published 2021)