Self-Assembly of Supramolecular Light-Harvesting Arrays from Symmetric Perylene-3,4-dicarboximide Trefoils
2015-12-17T01:55:50Z (GMT) by
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.