The Role of the Core Attachment Positioning in Triggering Intramolecular Singlet Exciton Fission in Perylene Diimide Tetramers

Previous studies have proposed that the presence of a flexible π-bridge linker is crucial in activating intramolecular singlet exciton fission (iSEF) in multichromophoric systems. In this study, we report the photophysical properties of three analogous perylene diimide (PDI) dendritic tetramers showing flexible/twisted π-bridged structures with α- and β-substitutions and a rigid/planar structure with a β-fused ring (βC) connection to a benzodithiophene-thiophene (BDT-Th) core. The rigidity and enhanced planarity of βC lead to significant intramolecular charge transfer and triplet formation via an intersystem crossing pathway. Steady-state spectroscopic measurements reveal similar absorption and emission spectra for the α-tetramer and the parent PDI monomer. However, their fluorescence quantum yield is significantly different. The negligible fluorescence yield of the α-tetramer (0.04%) is associated with a competitive nonradiative decay pathway. Indeed, for this twisted compound in a high polar environment, a fast and efficient iSEF with a triplet quantum yield of 124% is observed. Our results show that the α-single-bond connections in the α compound are capable of interrupting the coupling among the PDI units, favoring iSEF. We propose that the formation of the double triplet (1[TT]) state is through a superposition of singlet states known as [S1S0][TT]CT, which has been suggested previously for pentacene derivatives. Using steady-state and time-resolved spectroscopic experiments, we demonstrate that the conformational flexibility of the linker itself is necessary but not sufficient to allow iSEF. For the case of the other twisted tetramer, β, the strong π-π co-facial interactions between the adjacent PDI units in its structure lead to excimer formation. These excimer states trap the singlet excitons preventing the formation of the 1[TT] state, thus inhibiting iSEF.