The self-electroluminescent (self-ECL) behaviors of tetraphenylethylene carboxyl derivatives (TPED-(COOH)x) during the anodic process are first reported in this work. This study establishes a genuine co-reactant-free self-ECL system driven by electrogenerated radical disproportionation, which is mechanistically distinct from classic annihilation and co-reactant-mediated ECL pathways. The self-ECL mechanism involves the disproportionation of electrogenerated TPED•+-(COO−)x radicals to directly populate a charge-transfer excited state, which then decays radiatively. The results of the structure-activity analysis indicate that the electronic structure (determined by the conjugation length and substitution position) and intermolecular packing interactions are more important than either the aggregation-induced emission property or the oxidation potential for self-ECL. Furthermore, numerous controlled experiments have confirmed that the carboxyl group is essential for triggering self-ECL and this strategy can be extended to other AIE molecules. Notably, 4″,4″″′,4″″″″,4″″″″″′-(ethene-1,1,2,2-tetrayl) tetrakis ([1,1′:4′,1″-terphenyl]-4-carboxylic acid) (H4TCTPE) achieved a high self-ECL efficiency of up to 411% (relative to Ru(bpy)32+, ΦECL = 5%). Under optimal experimental conditions, an immunosensor for superoxide dismutase 2 (SOD2) was constructed based on H4TCTPE, with a linear range of 0.01-100 ng/mL, a detection limit of 7.9 pg/mL, excellent selectivity, reproducibility, and stability, and was successfully applied to serum analysis. This work provides a theoretical basis and design principles for the development of next-generation self-ECL luminophores.
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