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 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.