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Picosecond to millisecond tracking of a photocatalytic decarboxylation reaction provides direct mechanistic insights

Research output: Contribution to journalArticle

Original languageEnglish
Article number5152 (2019)
Number of pages7
JournalNature Communications
DateSubmitted - 17 Jul 2019
DateAccepted/In press - 24 Oct 2019
DatePublished (current) - 13 Nov 2019


The photochemical decarboxylation of carboxylic acids is a versatile route to free radical intermediates for chemical synthesis. However, the sequential nature of this multi-step reaction renders the mechanism challenging to probe. Here, we employ a 100 kHz mid-infrared probe in a transient absorption spectroscopy experiment to track the decarboxylation of cyclohexanecarboxylic acid in acetonitrile-d3 over picosecond to millisecond timescales using a photooxidant pair (phenanthrene and 1,4-dicyanobenzene). Selective excitation of phenanthrene at 256 nm enables a diffusion-limited photoinduced electron transfer to 1,4-dicyanobenzene.  A measured time offset in the rise of the CO2 byproduct reports on the lifetime (520 ± 120 ns) of a reactive carboxyl radical in solution, and spectroscopic observation of the carboxyl radical confirms its formation as a reaction intermediate. Precise clocking of the lifetimes of radicals generated in situ by an activated C-C bond fission will pave the way for improving the photocatalytic selectivity and turnover.

    Research areas

  • Catalytic mechanisms, Reaction kinetics and dynamics, Photocatalysis

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