Formation of Supramolecular Polymers and Discrete Dimers of Perylene Bisimide Dyes Based on Melamine−Cyanurates Hydrogen-Bonding Interactions

Abstract

Melamine-linked perylene bisimide dyes (MPBIs) bearing an ethylene or trimethylene group as linker moieties were synthesized, and their self-aggregation and coaggregation with cyanurates through complementary triple hydrogen bonds have been investigated. UV/vis studies revealed that both the MPBIs self-assemble in nonpolar organic solvent through pi-pi stacking interaction between perylene cores, giving self-aggregates with nearly identical thermal stabilities. Upon addition of 1 equiv of cyanurate components, however, the stabilities of the resulting aggregates were dramatically changed between the two systems, suggesting the formation of different types of hydrogen-bonded supramolecular species. Dynamic light scattering and atomic force microscopic studies revealed that the system featuring ethylene linker moieties generates a discrete dimer of MPBI supported by two cyanurate molecules, whereas the system featuring trimethylene linker moieties affords extended supramolecular polymers hierarchically organizing into nanoscopic fibers. These results demonstrate that it is possible to obtain distinct supramolecular species by just changing the number of carbon atoms at the linker moieties of MPBI components. The present strategy for the fabrication of discrete or polymeric supramolecular assemblies should be applicable to other functional pi-conjugated molecules.