Singlet fission is a process whereby two triplet excitons can be produced from one photon, potentially increasing the efficiency of photovoltaic devices. Endothermic singlet fission is desired for a maximum energy-conversion efficiency, and such systems have been considered to form an excimer-like state with multiexcitonic character prior to the appearance of triplets. However, the role of the excimer as an intermediate has, until now, been unclear. Here we show, using 5,12-bis((triisopropylsilyl)ethynyl)tetracene in solution as a prototypical example, that, rather than acting as an intermediate, the excimer serves to trap excited states to the detriment of singlet-fission yield. We clearly demonstrate that singlet fission and its conjugate process, triplet-triplet annihilation, occur at a longer intermolecular distance than an excimer intermediate would impute. These results establish that an endothermic singlet-fission material must be designed to avoid excimer formation, thus allowing singlet fission to reach its full potential in enhancing photovoltaic energy conversion.
The excited-state dynamics of 6,13-bis(triisopropylsilylethynyl)pentacene is investigated to determine the role of excimer and aggregate formation in singlet fission in high-concentration solutions. Photoluminescence spectra were measured by excitation with the evanescent wave in total internal reflection, in order to avoid reabsorption effects. The spectra over nearly two magnitudes of concentration were nearly identical, with no evidence for excimer emission. Time-correlated single-photon counting measurements confirm that the fluorescence lifetime shortens with concentration. The observed rate constant grows at high concentrations, and this effect is modeled in terms of the hard-sphere radial distribution function. NMR measurements confirm that aggregation takes place with a binding constant of between 0.14 and 0.43 M–1. Transient absorption measurements are consistent with a diffusive encounter mechanism for singlet fission, with hints of more rapid singlet fission in aggregates at the highest concentration measured. These data show that excimers do not play the role of an emissive intermediate in exothermic singlet fission in solution and that, while aggregation occurs at higher concentrations, the mechanism of singlet fission remains dominated by diffusive encounters.
Triisopropylsilylethynyl-substituted acenes (TIPS-acenes) have received prominent attention in the field of singlet fission, the pentacene derivative being an exothermic singlet fission material, and the tetracene being a prototypical endothermic material. Little attention has been given to TIPS-anthracene, which is expected to exhibit exothermic triplet-triplet annihilation, despite literature reports to the contrary.We show that there is some evidence for singlet fission in TIPS-anthracene solutions, and that it does exhibit triplet-triplet annihilation. We apply anti-Stokes action spectroscopy to determine the upconversion efficiency of a composition of TIPS-anthracene and platinum octaethylporphyrin. At a bias equivalent to 0.86 suns, the composition exhibited an annihilation efficiency of 3.2%, which may be compared to diphenylanthracene, which yielded 9.2% under the same conditions. We attribute the low efficiency to a combination of a shorter triplet lifetime and low lying T 2 and T 3 states. The results are supported by ab initio quantum chemical calculations.
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