Connectivity Effects on the Kinetically Controlled Supramolecular Polymerization of Linear Scaffolds

The synthesis of linear benzo[1,2‐b:4,5‐b’]dithiophenes (BDTs, 1a and 1b ) and 4,4‐difuoro‐4‐bora‐3a,4a‐diaza‐s‐indacenes (BODIPYs, 2a and 2b ), featuring modified connectivity between the central linear core and peripheral side chains, is reported. The supramolecular polymerization of these systems under kinetic control has been investigated. All compounds studied can form seven‐membered, hydrogen‐bonded pseudocycles, which hinder the progression of supramolecular polymerization. Notably, we demonstrate that both the nature of the central core and the connectivity of the linker joining the BDT or BODIPY units to the solubilizing moieties significantly influence the self‐assembly kinetics. Among these, only compound 2b supports a successful seeded supramolecular polymerization (SSP), enabling accelerated conversion from monomeric to aggregated species. Finally, leveraging the geometric and electronic complementarity between the BDT and BODIPY cores, we have explored the copolymerization processes of 1a + 2a and 1b + 2b . The VT‐UV‐Vis studies carried out with these mixtures reveal the interaction of these units. Finally the seeded co‐assembly further corroborates the formation of supramolecular copolymers.