RESUMO
Herein we introduce chalcogen squares via selenadiazole motifs as a new class of dynamic supramolecular bonding interactions for the modification and control of soft matter materials. We showcase selenadiazole motifs in supramolecular networks of varying primary chain length prepared through polymerization using tandem step-growth/Passerini multicomponent reactions (MCRs). Compared to controls lacking the selenadiazole motif, these networks display increased glass transition temperatures and moduli due to the chalcogen bonding linkages formed between chains. These elastomeric networks were shown to autonomously heal at room temperature, retaining up to 83 % of the ultimate tensile strength. Lastly, we use post-polymerization modification via the Biginelli MCR to add selenadiazole motifs to narrowly dispersed polymers for controlled topology in solution. Chalcogen squares via selenadiazoles introduce an exciting exchange mechanism to the realm of dynamic materials.
RESUMO
We introduce a four component Passerini polymerization utilizing sterically bulky isocyanide monomers. Under typical Passerini conditions, bulky isocyanides do not react within standard Passerini reaction timescales (hours). We overcome this challenge via the unique physiochemical conditions present in a vortex fluidic device, reducing the reaction time to 2 h on average. Under these high-shear thin-film conditions, bulky isocyanides are readily incorporated into the multicomponent polymerization without the need of high-pressure or temperature. Finally, we demonstrate that the four component approach using functional cyclic anhydrides allows for post-polymerization modification.