Multiexcitonic Triplet Pair Generation in Oligoacene Dendrimers as Amorphous Solid‐State Miniatures

Abstract Singlet fission in organic semiconducting materials has attracted great attention for the potential application in photovoltaic devices. Research interests have been concentrated on identifying working mechanisms of coherent SF processes in crystalline solids as ultrafast SF is hailed for efficient multiexciton generation. However, as long lifetime of multiexcitonic triplet pair in amorphous solids facilitates the decorrelation process for triplet exciton extractions, a precise examination of incoherent SF processes is demanded in delicate model systems to represent heterogeneous structures. Heterogeneous coupling and energetics for SF were developed in our oligoacene dendrimers, which mimic complicated SF dynamics in amorphous solids. SF dynamics in dendritic structures was thoroughly investigated by time‐resolved spectroscopic techniques and quantum chemical calculations in respect of the relative orientation/distance between chromophores and though‐bond/‐space interactions.