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A new class of anion–π+ AIEgens based on ring-fused annulated oxazolium architectures is reported, which can be readily synthesized via a single-step dual C–H activation annulative π-extension (APEX) protocol from simple oxazolium salts. The crucial and decisive role of anion–π+ interactions in their solid-state structural arrangement was analyzed to correlate their tunable AIE features and solid-state quantum yields.

Graphical abstract: Annulated oxazolium anion–π+ AIEgens

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