Tailoring long-range superlattice chirality in molecular self-assemblies via weak fluorine-mediated interactions

Area of Science:

• Supramolecular Chemistry
• Materials Science
• Organic Chemistry

Background:

• Controllable fabrication of enantiospecific molecular superlattices is crucial for advanced materials.
• Understanding intermolecular interactions is key to designing molecular self-assemblies.

Purpose of the Study:

• To demonstrate tailored long-range superlattice chirality in molecular self-assemblies.
• To investigate the role of fluorine functionalization in chiral recognition patterns.

Main Methods:

• High-resolution scanning tunneling microscopy (STM) for observing molecular self-assemblies.
• Density functional theory (DFT) calculations to analyze intermolecular interactions.
• Synthesis and functionalization of hexaphenylbenzene-based enantiomers.

Main Results:

• Fluorine functionalization of hexaphenylbenzene derivatives induced distinct long-range chiral recognition patterns.
• Specific non-covalent interactions (F⋯π, C-H⋯F, F⋯F) were quantified and linked to enantiospecific organization.
• Tunable superlattice chirality was achieved by modifying intermolecular interactions.

Conclusions:

• Engineering weak non-covalent interactions offers a viable route to control chirality in supramolecular assemblies.
• Fluorine functionalization is an effective strategy for achieving enantiospecific molecular superlattices.
• This work provides fundamental insights for designing chiral materials with tailored properties.