Perfluorophenyl-phenyl interactions in fluorescent properties

Perfluorophenyl–phenyl (arene–perfluoroarene, AP) interactions have emerged as a unique class of noncovalent forces that play a decisive role in dictating molecular packing, folding, and excited-state processes. Unlike conventional π–π stacking, AP interactions arise from quadrupole complementarity between electron-rich and electron-deficient aromatics, offering a powerful tool for the rational design of optoelectronic and photofunctional materials. In this review, we highlight how AP interactions modulate optical anisotropy, charge transport, and photoresponsive behavior, and more specifically, how they contribute to fluorescent properties such as quantum yield enhancement, aggregation-induced emission control, and circularly polarized luminescence (CPL). We also discuss recent advances in leveraging AP interactions in crystal engineering, supramolecular assembly, and device applications ranging from organic photonics to bioimaging. By unifying the fundamental insights into emerging applications, this review aims to establish AP interactions as a central design principle for next-generation fluorescent functional materials. • Perfluorophenyl–phenyl interactions govern fluorescence efficiency and color. • AP interactions enable precise control of molecular packing and emission tuning. • Integration with halogen bonding yields high-efficiency and color-variable cocrystals. • AP-driven assemblies exhibit enhanced CPL and anisotropic optical responses. • Applications expand to photoresponsive and bio-compatible luminescent materials.