Circularly Polarized Luminescence in Chiral Aggregates: Dependence of Morphology on Luminescence Dissymmetry

The self-assembly of a chiral perylene bisimide bichromophoric derivative possessing a 1,1'-binaphthalene bridge was investigated by adopting two different methodologies, leading to the formation of aggregates with dissimilar morphologies. The chiral nature of the aggregated structures was optically probed with the help of circular dichroism (CD), vibrational circular dichroism (VCD), and circularly polarized luminescence (CPL). The one-dimensional aggregates formed in methylcyclohexane (MCH) exhibited twice the value of luminescence dissymmetry factor (glum) when compared with the spherical aggregates formed in chloroform at higher concentration. The summation of excitonic couplings between the individual chromophoric units in an aggregated system is responsible for the remarkably high luminescence dissymmetry exhibited by the chiral aggregates. The nanostructures could be successfully embedded into polymer films, leading to the fabrication of solid-state materials with high CPL dissymmetry that can find novel applications in chiroptical sensing, memory, and light-emitting devices based on organic nanoparticles.