Rational construction of perylene bisimide columnar superstructures with a biased helical sense

Abstract

Discotic supramolecular complexes bearing six perylene bisimide (PBI) chromophores were prepared by mixing monotopically triple-hydrogen-bonding melamines equipped with two PBI chromophores and two 3,7-dimethyloctyl chiral handles with tritopically triple-hydrogen-bonding cyanuric acid (CA). UV/Vis and fluorescence titration experiments demonstrated that the discotic complexes were formed in methylcyclohexane by the 3:1 complexation between the melamines and CA. TEM and AFM studies revealed that the complexes hierarchically organize into fibrous columnar assemblies, which eventually results in the formation of organogels. Circular dichroism (CD) and flash-photolysis time resolved microwave conductivity measurements revealed the presence of extended chiral stacks of PBI chromophores within the columns. The anisotropy factors of the columnar assemblies are remarkably high (g=1.5×10(-3)) when considering the presence of only one 3,7-dimethyloctyl chiral handle per perylene chromophore, suggesting that the columnar structures have a biased helical sense. The fact that the chiral centers are located inside the discotic complexes rather than at their peripheries might be unique structural property responsible for the rather strong optical activities for the assemblies of this chromophore. The effective transcription of the molecular chirality to the extended columnar assemblies through the formation of unique discotic complexes enables the expression of "majority-rules" chiral amplification effect, which is unprecedented for the supramolecular assemblies of PBIs.