Sweet Spot of Intermolecular Coupling in Crystalline Rubrene: Intermolecular Separation to Minimize Singlet Fission and Retain Triplet–Triplet Annihilation

Abstract

Singlet fission is detrimental to NIR-to-vis photon upconversion in the solid rubrene (Rub) films, as it diminishes photoluminescence efficiency. Previous studies have shown that thermally activated triplet energy transport drives singlet fission with nearly 100% efficiency in closely packed Rub crystals. Here, we examine triplet separation and recombination as a function of intermolecular distance in the crystalline films of Rub and the <i>t</i>-butyl substituted rubrene (<i>t</i>BRub) derivative. The increased intermolecular distance and altered molecular packing in <i>t</i>BRub films cause suppressed singlet dissociation into free triplets due to slower triplet energy transport. It was found that the formation of correlated triplet pairs ¹(TT) and partial triplet separation ¹(T···T) occurs in both Rub and <i>t</i>BRub films despite differences in intermolecular coupling. Under weak intermolecular coupling as in <i>t</i>BRub, geminate triplet annihilation of ¹(T···T) outcompetes dissociation into free triplets, resulting in emission from the ¹(TT) state. Essentially, increasing intermolecular distance up to a certain point (a sweet spot) is a good strategy for suppressing singlet fission and retaining triplet-triplet annihilation properties.