Exploring the Spatial Arrangement of <i>C</i>_s-Symmetric Boron Subphthalocyanine Hybrid Crystals by Tuning Arene–Perfluoroarene Interactions

Manipulating the solid-state arrangements of organic electronic materials can profoundly impact the performance of the devices in which they are utilized. This study investigates how π–π interactions, notably arene-perfluoroarene (πH···πF) interactions, guide the crystal structures of boron subphthalocyanine (BsubPc) hybrid derivatives by leveraging the dual dipole moments inherent in F8BsubPcs and F8Bsub(Pc2–Nc1)s. We crafted a simple molecular design varying BsubPc-type hybrids by their axial moieties and number of peripheral arene sites while maintaining a consistent count of peripheral perfluoroarene (π–hole) sites. The geometric analyses revealed that solid-state arrangements of perfluorinated BsubPc-type hybrids can be purposefully altered by introducing substituents that promote πH···πF stacking. We found that an additional fused benzene ring in the periphery introduced new stacking modes characterized by enhanced π–π overlap in F8Bsub(Pc2–Nc1) hybrids compared to F8BsubPcs, producing one-dimensional slip-stacked columns directed by strong-to-moderate πH···πF interactions. Incorporation of an axial phenol ligand in the F8Bsub(Pc2-Nc1) architecture further directed new stacking patterns, transforming the framework of arene-perfluoroarene interactions from their axially halogenated counterparts. Long-range packing motifs, Hirshfeld surfaces, various solvent growth methods, serendipitous ring-opened structures, and halogen bonding were examined to understand these πH···πF interactions further. This work realizes the control of BsubPc hybrid spatial arrangements through strategic π–π interactions and provides avenues for potentially improved electronic functionality via highly ordered close packing configurations.