Noncovalent synthesis of homo and hetero-architectures of supramolecular polymers via secondary nucleation.

The synthesis of supramolecular polymers with controlled architecture is a grand challenge in supramolecular chemistry. Although living supramolecular polymerization via primary nucleation has been extensively studied for controlling the supramolecular polymerization of small molecules, the resulting supramolecular polymers have typically exhibited one-dimensional morphology. In this report, we present the synthesis of intriguing supramolecular polymer architectures through a secondary nucleation event, a mechanism well-established in protein aggregation and the crystallization of small molecules. To achieve this, we choose perylene diimide with 2-ethylhexyl chains at the imide position as they are capable of forming dormant monomers in solution. Activating these dormant monomers via mechanical stimuli and hetero-seeding using propoxyethyl perylene diimide seeds, secondary nucleation event takes over, leading to the formation of three-dimensional spherical spherulites and scarf-like supramolecular polymer heterostructures, respectively. Therefore, the results presented in this study propose a simple molecular design for synthesizing well-defined supramolecular polymer architectures via secondary nucleation.

Post-synthetic π-extension of perylene conjugated porous polymer via APEX reactions: tunable optical and gas storage properties.

Double post-synthetic modification is used for the π-extension of perylene based conjugated porous polymers (CPPs) using sequential annulative π-extension (APEX) reactions. This approach enabled us to synthesize new CPPs rendered with donor-acceptor rigid π-systems such as benzoperylene anhydride (BPA-CPP) and benzoperylene benzimidazole (BPBI-CPP) with distinct optical properties. Despite its low surface area, BPBI-CPP shows good CO2 uptake and pH responsive behaviour owing to the presence of benzimidazole rings.