Synthesis and predetermined supramolecular chirality of carbohydrate-functionalized perylene bisimide derivatives.

Eight carbohydrate-modified perylene bisimides (PBI-4 lac-2 lac, PBI-4 lac-2 Man, PBI-4 lac-2 Gal, PBI-4 lac-2 Mal, PBI-4 Man-2 Man, PBI-4 Man-2 lac, PBI-4 Man-2 Gal and PBI-4 Man-2 Mal) were synthesized, and the following predetermined supramolecular chirality rule was found: perylene bisimides modified with disaccharides (D-lactose and D-maltose) at the imide position generated right-handed chirality, and those modified with monosaccharides (D-mannose and D-galactose) generated left-handed chirality, when D-lactose or D-mannose was substituted in the bay positions of perylene bisimides with amide bonds as the linking spacers. These results may be because of the difference in the stacking angle of the perylene bisimide backbones induced by the steric effect and the additional hydrogen bonds between the disaccharide residues. This study provides an important design rule for predetermined chiral self-assembly of perylene bisimides.