Quantum interference effects elucidate triplet-pair formation dynamics in intramolecular singlet-fission molecules.

Quantum interference (QI)-the constructive or destructive interference of conduction pathways through molecular orbitals-plays a fundamental role in enhancing or suppressing charge and spin transport in organic molecular electronics. Graphical models were developed to predict constructive versus destructive interference in polyaromatic hydrocarbons and have successfully estimated the large conductivity differences observed in single-molecule transport measurements. A major challenge lies in extending these models to excitonic (photoexcited) processes, which typically involve distinct orbitals with different symmetries. Here we investigate how QI models can be applied as bridging moieties in intramolecular singlet-fission compounds to predict relative rates of triplet pair formation. In a series of bridged intramolecular singlet-fission dimers, we found that destructive QI always leads to a slower triplet pair formation across different bridge lengths and geometries. A combined experimental and theoretical approach reveals the critical considerations of bridge topology and frontier molecular orbital energies in applying QI conductance principles to predict rates of multiexciton generation.

Wave Function Based Analysis of Dynamics versus Yield of Free Triplets in Intramolecular Singlet Fission.

Experiments in several intramolecular singlet fission materials have indicated that the triplet-triplet spin biexciton has a much longer lifetime than believed until recently, opening up loss mechanisms that can annihilate the biexciton prior to its dissociation to free triplets. We have performed many-body calculations of excited state wave functions of hypothetical phenylene-linked anthracene molecules to better understand linker-dependent behavior of dimers of larger acenes being investigated as potential singlet fission candidates. The calculations reveal unanticipated features that we show carry over to the real covalently linked pentacene dimers. Dissociation of the correlated triplet-triplet spin biexciton and free triplet generation may be difficult in acene dimers where the formation of the triplet-triplet spin biexciton is truly ultrafast. Conversely, relatively slower biexciton formation may indicate smaller spin biexciton binding energy and greater yield of free triplets. Currently available experimental results appear to support this conclusion. Whether or not the two distinct behaviors are consequences of distinct mechanisms of triplet-triplet generation from the optical singlet is an interesting theoretical question.