Vibrational Energy Transfer in Organic Semiconductors Revealed by Infrared Pump–Probe Spectroscopy

Phonon engineering has improved charge transport in semiconducting organic molecules by introducing high mass side chains, which ameliorate harmful transient localization. The influence of these side chains on thermal energy transfer and dynamic disorder has not been fully explored. In this work, we first use low temperature X-ray diffraction to probe thermally induced structural changes in functionalized acene molecular semiconductors, combined with low temperature IR spectroscopy to track changes to their vibrational energy landscape. Furthermore, time-resolved IR pump-IR probe spectroscopy is employed to measure IR absorption kinetics associated with the high mass side chains of molecules, revealing intramolecular vibrational energy redistribution pathways. Alkyne groups in the side chains are shown to act as vibrational energy traps, remaining hot for time scales of >2 ns. The results reveal nonequilibrium vibrational pathways associated with side chains that may influence the phonon manifold relevant to dynamic disorder.