Exploring the Spatial Arrangement of Cs-Symmetric Boron Subphthalocyanine Hybrid Crystals by Tuning Arene–Perfluoroarene Interactions

Abstract

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 (π_H···π_F) 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 π_H···π_F 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 π_H···π_F 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 π_H···π_F 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.