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Updated: Oct 13, 2025

Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems
Published on: February 10, 2020
Femtosecond photodecarbonylation of photo-ODIBO studied by stimulated Raman spectroscopy and density functional
Learnmore Shenje1, Yingqi Qu1, Vladimir Popik2
1Department of Physics and Astronomy, University of Georgia, Athens, Georgia 30602, USA. ullrich@uga.edu.
Abstract:
Photo-oxa-dibenzocyclooctyne (Photo-ODIBO) undergoes photodecarbonylation under UV excitation to its bright S2 state, forming a highly reactive cyclooctyne, ODIBO. Following 321 nm excitation with sub-50 fs actinic pulses, the excited state evolution and cyclopropenone bond cleavage with CO release were characterized using femtosecond stimulated Raman spectroscopy and time-dependent density functional theory Raman calculations. Analysis of the photo-ODIBO S2 CO Raman band revealed multi-exponential intensity, peak splitting and frequency-shift dynamics. This suggests a stepwise cleavage of the two C-C bonds in the cyclopropenone structure that is completed within <300 fs after excitation. Evidence of intramolecular vibrational relaxation on the S2 state, concurrent with photodecarbonylation, with dynamics matching previous electronic transient absorption spectroscopy, was also observed. This confirms an excited state, as opposed to ground state, photodecarbonylation mechanism resulting in a vibronically excited photoproduct, ODIBO.
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