Crystal Engineering of 1D Exciton Systems Composed of Single‐ and Double‐Stranded Perylene Bisimide J‐Aggregates

Single crystals of three at bay area tetraphenoxy-substituted perylene bisimide dyes are grown by vacuum sublimation. X-ray analysis reveals the self-assembly of these highly twisted perylene bisimides (PBIs) in the solid state via imide-imide hydrogen bonding into hydrogen-bonded PBI chains. The crystallographic insights disclose that the conformation and sterical congestion imparted by the phenoxy substituents can be controlled byortho-substituents. Accordingly, whilst sterically less demanding methyl and isopropyl substituents afford double-stranded PBI chains of complementaryPandMatropo-enantiomers, single hydrogen-bonded chains of homochiral PBIs are observed for the sterically more demandingortho-phenyl substituents. Investigation of the absorption and fluorescence properties of microcrystals and thin films of these PBIs allow for an unambiguous interpretation of these exciton systems. Thus, the J-aggregates of the double-stranded crystals exhibit a much larger (negative) exciton coupling than the single-stranded one, which in contrast has the higher solid-state fluorescence quantum yield.