Multi-scale assembly strategies driven by arene-perfluoroarene interaction: molecular design of functional materials

The arene-perfluoroarene (AP) interaction, arising between polyaromatic hydrocarbons and their perfluorinated counterparts, features an inverted electron distribution induced by fluorination compared to hydrocarbons. This interaction exhibits enhanced binding affinity compared to conventional π-π interaction and has emerged as a powerful tool for directing self-assembly processes to fabricate functional materials. This review outlines two construction strategies for AP systems: (1) covalent integration of electron-rich (arene) and electron-deficient (perfluoroarene) moieties within a single building block and (2) assembly of discrete complementary components separately functionalized with arene and perfluoroarene units. The structural diversity of supramolecular architectures driven by the AP interaction is analyzed, emphasizing their programmable geometries and electronic properties. Furthermore, we systematically summarize the applications of AP interaction directed assemblies in photoelectric devices and circularly polarized luminescent (CPL) materials, where tailored intermolecular AP interactions optimize the optoelectronic performance. We also highlight their application in synthetic chemistry and recognition. This review underscores the versatility of AP interactions as a design principle for advanced functional materials, bridging supramolecular chemistry with interdisciplinary applications in materials science, catalysis, and biomedicine.