Direct observation of long-range chirality transfer in a self-assembled supramolecular monolayer at interface in situ

Abstract

Due to the interest in the origin of life and the need to synthesize new functional materials, the study of the origin of chirality has been given significant attention. The mechanism of chirality transfer at molecular and supramolecular levels remains underexplored. Herein, we study the mechanism of chirality transfer of N, N’-bis (octadecyl)-L-/D-(anthracene-9-carboxamide)-glutamic diamide (L-/D-GAn) supramolecular chiral self-assembled at the air/water interface by chiral sum-frequency generation vibrational spectroscopy (chiral SFG) and molecular dynamics (MD) simulations. We observe long-range chirality transfer in the systems. The chirality of Cα-H is transferred first to amide groups and then transferred to the anthracene unit, through intermolecular hydrogen bonds and π-π stacking to produce an antiparallel β-sheet-like structure, and finally it is transferred to the end of hydrophobic alkyl chains at the interface. These results are relevant for understanding the chirality origin in supramolecular systems and the rational design of supramolecular chiral materials.

Supramolecular Chemistry: Exploring the Use of Electronic Structure, Molecular Dynamics, and Machine Learning Approaches

“…In 2022, Zhang et al. have used MD simulations to understand chirality transfer at the formation of supramolecular aggregates of N , N ’‐bis(octadecyl)‐ L / D ‐(anthracene‐9‐carboxamide)‐glutamic diamide ( L / D ‐ GAn) [60] . The simulations unequivocally demonstrate that L / D ‐GAn self‐assembles at the air/water interface, forming nanorods (Figure 10c–d).…”

Probing the adsorption configuration of methanol at a charged air/aqueous interface using nonlinear spectroscopy

“…The magic angle should not affect the main conclusions drawn from SFG orientational analysis. 62,63 Compared to the pure water surface, the orientation angle of CH 3 at the surface of the 0.1 M HClO 4 electrolyte solution decreased by 6.41, which was insufficient to compensate for the 8.2% decrease in the oscillator strength of CH 3 . In contrast, the orientation angle of CH 3 at the surface of the 0.1 M NaClO 4 electrolyte solution increased by 15.51, with only a marginal 2.6% decrease in the oscillator strength.…”

Chiral structures in azobenzene‐containing systems: Construction, regulation, and application

“…The achiral components are assembled with noncovalent bonding interactions for one-handed helical excess to form supramolecular assemblies in which a certain helical conformation prevails. [123][124][125] These chiral supramolecular structures exhibit dynamically tunable properties, with their helicity being regulated by environmental conditions or external stimuli. [126] Chiral induction not only avoids the use of expensive chiral monomers but also eliminates the need for more complex synthetic processes such as asymmetric catalysis and enantioselective polymerization.…”

“…In particular, chiral solvation induction, [112–114] chiral dopant induction, [115,116] CPL induction, [117] chiral gel induction [118–120] and host–guest chiral induction [121,122] have been successfully used to produce chiral supramolecular structures from achiral systems. The achiral components are assembled with noncovalent bonding interactions for one‐handed helical excess to form supramolecular assemblies in which a certain helical conformation prevails [123–125] . These chiral supramolecular structures exhibit dynamically tunable properties, with their helicity being regulated by environmental conditions or external stimuli [126] .…”