Organic dyads and triads based on the triphenylene-rylenediimide couple: Molecular design, self-organization, and photo-physical properties

Abstract

Liquid-crystalline D-A dyads and A-D-A triads, based on the chemical association of electron-donor (D) triphenylene discogens and electron-acceptor (A) perylene/benzoperylene diimides, have been synthesized by the Pd-catalyzed Sonogashira coupling/DBU-promoted cyclization reactions tandem. These molecular heterojunctions spontaneously self-organize into columnar hexagonal (Colhex) or/and rectangular (Colrec) mesophases, over broad temperature ranges including room temperature, with the antagonist moieties segregated into alternated homo-molecular (homolithic) stacks within mixed columns. Their intramolecular electron and energy transfers have been studied by UV/Vis absorption and fluorescence emission spectroscopies. Due to photo-induced electron transfer between donor and acceptor units, fluorescence quenching is systematically observed for all the dyads and triads. This study further reveals that perylenediimide is a stronger electron acceptor than the larger benzoperylenediimide building block. Density function theory calculations of their molecular structures and HOMO-LUMO energy levels and gaps support the experimental results and demonstrate that these donor-acceptor systems have potential applications in various optoelectronic devices.