Cross‐Transition‐Dipole Stacking of Conjugated Organic Molecules: Structure, Exciton Behavior and Optoelectronic Property

Abstract Organic conjugated molecules have gained widespread application as organic semiconductors due to their unique optoelectronic properties. The rigidity of these large conjugated structures facilitates strong intermolecular interactions, which significantly influence their properties in the solid state through various molecular arrangements. The study of the relationship among molecular arrangement, exciton behavior, and optoelectronic properties is an eternal research topic. Cross‐dipole stacking is a specific molecular arrangement that demonstrates unique characteristics and has received continuous attention over the past decades. This mini‐review will first discuss the unique exciton behaviors in cross‐dipole stacking based on exciton models, including weak exciton coupling and suppression of Förster resonance energy transfer. These exciton behaviors, determined by molecular stacking arrangements, are fundamental to the optoelectronic properties of cross‐dipole stacking systems. Next, we will introduce well‐defined cross‐dipole systems and summarize their design principles from a molecular structure perspective. Finally, we will present the specific optoelectronic properties of cross‐dipole stacking systems and their outstanding performance, such as high solid‐state luminescence, good charge carrier mobility, and significant CD/CPL. Through this mini‐review, we hope to enhance the understanding of cross‐dipole stacking, contributing to the construction of such systems, the exploration of excited‐state behaviors, and the discovery of high‐performance materials.