Self-Assembly of Supramolecular Light-Harvesting Arrays from Symmetric Perylene-3,4-dicarboximide Trefoils

Unlike the widely studied perylene-3,4:9,10-bis­(dicarboximide) (PDI) dyes, self-assembly of the corresponding perylene-3,4-dicarboximide (PMI) dyes into large arrays and studies of their excited state properties have received far less attention. Two symmetric PMI trefoils were synthesized by connecting the 9-position of the perylene core either directly (1) or through a phenylene linker (2) to the 1,3,5-positions of a central benzene ring. Synchrotron-based small- and wide-angle X-ray scattering measurements in methylcyclohexane show that trefoil 1 self-assembles into cofacial trimers (1₃) on average, while trefoil 2 forms much larger assemblies that are tridecamers (2₁₃) on average. Their photophysics were characterized using steady-state as well as transient absorption and emission spectroscopy. Time-resolved spectroscopy reveals that both 1₃ and 2₁₃ initially form excitonically coupled excited states that subsequently relax to excimer states having 20 and 8.4 ns lifetimes, respectively, which decay to ground-state primarily nonradiatively. The data are consistent with stronger electronic coupling between the PMI molecules in 2₁₃ relative to 1₃.