Pathway-dependent supramolecular polymerization by planarity breaking

In controlled supramolecular polymerization, planar π-conjugated scaffolds are commonly used to predictably regulate stacking interactions, with various assembly pathways arising from competing interactions involving side groups. However, the extent to which the nature of the chromophore itself (planar vs. non-planar) affects pathway complexity requires clarification. To address this question, we herein designed a new BOPHY dye 2, where two oppositely oriented BF₂ groups induce a disruption of planarity, and compared its supramolecular polymerization in non-polar media with that of a previously reported planar BODIPY 1 bearing identical substituents. The slightly non-planar structure of the BOPHY dye 2, as evident in previously reported X-ray structures, together with the additional out-of-plane BF₂ group, allow for more diverse stacking possibilities leading to two fiber-like assemblies (kinetic 2A and thermodynamic 2B), in contrast to the single assembly previously observed for BODIPY 1. The impact of the less rigid, preorganized BOPHY core compared to the planar BODIPY counterpart is also reflected in the stronger tendency of the former to form anisotropic assemblies as a result of more favorable hydrogen bonding arrays. The structural versatility of the BOPHY core ultimately enables two stable packing arrangements: a kinetically controlled antiparallel face-to-face stacking (2A), and a thermodynamically controlled parallel slipped packing (2B) stabilized by (BF₂) F⋯H (meso) interactions. Our findings underscore the significance of planarity breaking and out-of-plane substituents on chromophores as design elements in controlled supramolecular polymerization.