Precise Modulation of Intramolecular Aggregation‐induced Electrochemiluminescence by Tetraphenylethylene‐based Supramolecular Architectures

Abstract The precisely modulated synthesis of programmable light‐emitting materials remains a challenge. To address this challenge, we construct four tetraphenylethylene‐based supramolecular architectures (SA, SB, SC, and SD), revealing that they exhibit higher electrochemiluminescence (ECL) intensities and efficiencies than the tetraphenylethylene monomer and can be classified as highly efficient and precisely modulated intramolecular aggregation–induced electrochemiluminescence (PI‐AIECL) systems. The best‐performing system (SD) shows a high ECL cathodic efficiency exceeding that of the benchmark tris(2,2′‐bipyridyl)ruthenium(II) chloride in aqueous solution by nearly six‐fold. The electrochemical characterization of these architectures in an organic solvent provides deeper mechanistic insights, revealing that SD features the lowest electrochemical band gap. Density functional theory calculations indicate that the band gap of the guest ligand in the SD structure is the smallest and most closely matched to that of the host scaffold. Finally, the SD system is used to realize ECL‐based cysteine detection (detection limit=14.4 nM) in real samples. Thus, this study not only provides a precisely modulated supramolecular strategy allowing chromophores to be controllably regulated on a molecular scale, but also inspires the programmable synthesis of high‐performance aggregation‐induced electrochemiluminescence emitters.