Engineering Perfluoroarenes for Enhanced Molecular Barrier Effect and Chirality Transfer in Solutions

Noncovalent forces express significant impact on the photophysical properties, and flexible employment of weak forces facilitates the design of novel luminescent materials with a variety of applications. Arene-perfluoroarene (AP) force, as one of the π-hole/π interaction, shows unique directionality, involving an electron-deficient π-hole interacting with a π-electron-rich region, facilitating precise orientation and stabilization in supramolecular structures. Here we present an amination engineering protocol to build a perfluoroarene library based on octafluoronaphthalene skeleton with varied steric and electronic properties. In diluted solution-based assemblies, the perfluoroarenes perform as efficient molecular barrier to perylene building units, lighting up the luminescence. Enhanced steric effects, hydrophobicity and appended aromatic pendants are pivotal structural factors to boost the molecular barrier effect. Highly affinitive AP coassemblies transfer chirality from perfluoroarenes to achiral perylene moieties, inducing the appearance of chiral microstructures with tailored circularly polarized luminescence. The applications as luminescent ink for enhanced water-resistance in displays and anti-counterfeiting are successfully realized. This work greatly extended the potentials of molecular engineering in noncovalently bonded luminescent materials, and clearly unveil the structure-property correlations.