Issue 45, 2021

Femtosecond photodecarbonylation of photo-ODIBO studied by stimulated Raman spectroscopy and density functional theory

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 C[double bond, length as m-dash]O 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.

Graphical abstract: Femtosecond photodecarbonylation of photo-ODIBO studied by stimulated Raman spectroscopy and density functional theory

Supplementary files

Article information

Article type
Paper
Submitted
30 jul 2021
Accepted
03 nov 2021
First published
16 nov 2021

Phys. Chem. Chem. Phys., 2021,23, 25637-25648

Author version available

Femtosecond photodecarbonylation of photo-ODIBO studied by stimulated Raman spectroscopy and density functional theory

L. Shenje, Y. Qu, V. Popik and S. Ullrich, Phys. Chem. Chem. Phys., 2021, 23, 25637 DOI: 10.1039/D1CP03512F

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