Halogenation Regulates Supramolecular Chirality at Hierarchical Levels of Self-Assembled N-Terminal Aromatic Amino Acids

Halogenation brings about dramatic variations to the performance of self-assembled organic species, such as luminescence and crystallinity, but it has seldom been utilized for chirality control. Here we show the halogenation effect of self-assembling organic building units on supramolecular chirality and chiroptical responses. N-terminal aromatic amino acids with different substituted halogen atoms at p-phenylalanine residues self-assembled into one-dimensional fibrous structures. Halogenation induced the emergence of macroscopic chirality regardless of halogen properties like electronegativity, generating exclusive homochiral helical structures. Solid-state X-ray structures and time-dependent density functional theory were utilized for calculated electronic circular dichroism spectra, which evidenced the diverse driving forces to enable chiral molecular arrangements, including H-bonds and halogen bonds. Red-shifted luminescence was observed in brominated building units, giving rise to active circularly polarized luminescence. This work elucidates the multiple roles of halogen in chiral self-assembly systems, which provides insight into the rational control over supramolecular chirality and their chiroptical applications.

Automated summary

The addition of halogens in self-assembled organic structures induces the emergence of chiral structures, generating exclusive homochiral helical structures regardless of the properties of the halogens. Experimental and theoretical studies elucidate the role of halogens in chiral self-assembly systems, providing insights into the rational control over supramolecular chirality and their applications in chiroptics.