Boosting Electrochemiluminescence in Ring‐Contracted Porphyrins via Central‐Coordination Modulation

Herein, a stepwise central‐coordination strategy to engineer corrole‐based electrochemiluminescence (ECL), achieving enhanced ECL with low triggering potentials and efficient emission in aqueous media, is reported. Aluminum insertion and axial pyridine coordination of free‐base meso ‐tris(pentafluorophenyl)corrole ( TPFC ) generate mono‐pyridine Al(III) TPFC ( Al‐TPFC ), which exhibits improved redox reversibility, reduced oxidation potentials, and a 24‐fold ECL enhancement with dual‐peak emission. Controlled conversion to bis‐pyridine Al(III) TPFC ( Al‐TPFC‐PY ) enables emission redshift and intensity modulation. Theoretical calculations identify ligand‐based locally excited states as the emission origin, emphasizing the crucial role of Al(III) in luminescence enhancement. Bovine serum albumin‐functionalized Al‐TPFC nanoparticles exhibit over 40‐fold higher ECL intensity in aqueous solution compared to TPFC nanoparticles, with further improvement achieved through tetraphenylethylene incorporation to suppress π–π stacking. This study establishes a coordination‐modulated ECL platform using ring‐contracted porphyrins, advancing both fundamental understanding and practical applications of ECL in functional π‐systems.