A Thermally Activated Delayed Fluorescence Emitter Investigated by Time-Resolved Near-Infrared Spectroscopy.

Emitters for organic light-emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) require small singlet (S1 )-triplet (T1 ) energy gaps as well as fast intersystem crossing (ISC) transitions. These transitions can be mediated by vibronic mixing with higher excited states Sn and Tn (n=2, 3, 4, …). For a prototypical TADF emitter consisting of a triarylamine and a dicyanobenzene moiety (TAA-DCN) it is shown that these higher states can be located energetically by time-resolved near-infrared (NIR) spectroscopy.

Environment-Driven Coherent Population Transfer Governs the Ultrafast Photophysics of Tryptophan.

By combining UV transient absorption spectroscopy with sub-30-fs temporal resolution and CASPT2/MM calculations, we present a complete description of the primary photoinduced processes in solvated tryptophan. Our results shed new light on the role of the solvent in the relaxation dynamics of tryptophan. We unveil two consecutive coherent population transfer events involving the lowest two singlet excited states: a sub-50-fs nonadiabatic La → Lb transfer through a conical intersection and a subsequent 220 fs reverse Lb → La transfer due to solvent-assisted adiabatic stabilization of the La state. Vibrational fingerprints in the transient absorption spectra provide compelling evidence of a vibronic coherence established between the two excited states from the earliest times after photoexcitation and lasting until the back-transfer to La is complete. The demonstration of response to the environment as a driver of coherent population dynamics among the excited states of tryptophan closes the long debate on its solvent-assisted relaxation mechanisms and extends its application as a local probe of protein dynamics to the ultrafast time scales.