Theoretical insights into aggregation-induced helicity modulation of a perylene bisimide derivative
Formation of helical chiroptical self-assemblies via noncovalent interaction is a widely observed phenomenon in nature, the mechanism of which remains insufficiently understood. Employing an amphiphilic perylene–sugar dyad molecule (PBI-HAG) as an example, we report that the modulatable supramolecular helicity may emerge from an aggregating process that is dominated by competition between two types of noncovalent interaction: hydrogen bonding and π–π stacking. The interplay between these two driving forces, which is greatly affected by the solvent environment, determines the morphology the supramolecular assembly of PBI-HAGs. In particular, a non-layered supramolecular structure was formed in octane owing to stabilization effects of intermolecular hydrogen bonds, whereas a layered supramolecular structure was formed in water because of energetically favorable π–π stacking of aromatic rings. The formation of distinct supramolecular architectures in different solvents was reinforced by simulated circular dichroism spectra, which show opposite signals consistent with experimental observations. The results of this study could help us understand aggregation-induced supramolecular chirality of noncovalent self-assemblies.
KeywordsSupramolecular helicity Aggregation-induced chirality Self-assembly Circular dichroism Exciton model
We acknowledge financial support by the National Natural Science Foundation of China (Grant Nos. 21503186, 21674032).
X.L. designed the study. X.L. and L.L. carried out the calculations, analyzed the data and wrote the paper.
Compliance with ethical standards
Competing financial interests
The authors declare no competing financial interest.
- 35.Ogi S, Stepanenko V, Sugiyasu K, Takeuchi M, Würthner F (2015) Mechanism of self-assembly process and seeded Supramolecular polymerization of perylene bisimide organogelator. J Am Chem Soc 137:3300–3307Google Scholar
- 43.Würthner F, Chen Z, Dehm V, Stepanenko V (2006) One-dimensional luminescent nanoaggregates of perylene bisimides. Chem Commun 1188–1190Google Scholar
- 54.Allen MP, Tildesley DJ (1989) Computer simulation of liquids. Oxford University Press, OxfordGoogle Scholar
- 58.Dunning Jr TH (1977) PJ Hay in modern theoretical chemistry. Plenum, New YorkGoogle Scholar
- 59.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA (2015) Gaussian 09, revision A. 02, vol 2009. Gaussian, Inc, WallingfordGoogle Scholar