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 CO uptake and pH responsive behaviour owing to the presence of benzimidazole rings.
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