Dynamic emissive signatures of intramolecular singlet fission during equilibration to steady state revealed from stochastic kinetic simulations.

We investigate the ability of dynamic fluorescence probes to accurately track populations of multi-excitonic states in molecular dyads based on conjugated acenes capable of intramolecular singlet fission (iSF). Stochastic simulations of reported photophysical models from time-resolved spectroscopic studies of iSF dyads based on large acenes (e.g., tetracene and pentacene) are used to extrapolate population and fluorescence yield dynamics. The approach entails the use of repetitive rectangular-shaped excitation waveforms as a stimulus, with durations comparable to triplet lifetimes. We observe unique dynamics signatures that can be directly related to relaxation of multi-exciton states involved over the entire effective time of singlet fission in the presence and absence of an excitation light stimulus. In particular, time-dependent fluorescence yields display an abrupt decay followed by slower rise dynamics appearing as a prominent "dip" feature in responses. The initial fast decrease in the fluorescence yield arises from the formation of triplet pairs and separated triplets that do not produce emission resembling a complete ground state bleach effect. However, relaxation of one separated triplet allows the system to absorb, and in some cases, this increases the fluorescence yield, causing rise dynamics in the emissive response. Our approach also permits extrapolation of all multi-exciton state population dynamics up to steady state conditions in addition to the ability to explore consequences of alternative relaxation channels. The results demonstrate that it is possible to resolve unique signatures of singlet fission events from dynamic fluorescence studies, which can augment detection capabilities and extend sensitivity limits and accessible time scales.