The development of highly active, eco-friendly, and structurely fine-tunable organic luminophores is currently desirable for electrochemiluminescence (ECL). Tetraphenylethene (TPE) derivatives are the most representative aggregation-induced emission characteristic (AIEgens). In contrast, their aggregation-induced ECLs have not been detail studied. Herein, we report the bright cathodic aggregated state ECL of TPE derivatives by a coreactant approach. In this system, the substituents profoundly affect ECL emissions by changing the relative intensities of R and B band intensity ratios in their UV–vis spectra as well as the HOMO and LUMO energies. It was discovered that electron-withdrawing nitro-substituted TPE-(NO2)4 with a smaller LUMO/HOMO band gap and stronger R band featured the strongest ECL emissions and became the best luminophore for the highly efficient detection of iodide (I–) in the aqueous phase. This work not only reveals the influence of R and B bands in TPE derivative UV–vis spectra on their optical properties but also constructs a novel aggregation-induced ECL sensing.

By af acile peripheral decoration of 5-(4-aminophenyl)-10,15,20-triphenylporphyrin (ATPP) with inherent aggregation-induced emission (AIE) active tetraphenylethene (TPE), av ersatile AIEgenic porphyrin derivative (ATPP-TPE) was obtained, whichgreatly abolishes the detrimental pp stacking and thus surmounts the notorious aggregationcaused quenching (ACQ) effect of ATPP in aqueous phase. The photoluminescence of ATPP-TPE is 4.5-fold stronger than ATPP at aggregation state.M oreover,a nu nequivocal aggregation induced electrochemiluminescence (AIECL) of ATPP-TPE was found to be seriously dependent on its aggregation property in aqueous solution with efficiency of 34 %, which is 6times higher than pure ATPP.The versatility of this molecular structure modulation strategy along with the ACQ-to-AIE transformation in this work provides direction to guide for applying liposoluble porphyrins in aqueous phase by designs of synthetic porphyrin AIEgens.

By af acile peripheral decoration of 5-(4-aminophenyl)-10,15,20-triphenylporphyrin (ATPP) with inherent aggregation-induced emission (AIE) active tetraphenylethene (TPE), av ersatile AIEgenic porphyrin derivative (ATPP-TPE) was obtained, whichgreatly abolishes the detrimental pp stacking and thus surmounts the notorious aggregationcaused quenching (ACQ) effect of ATPP in aqueous phase. The photoluminescence of ATPP-TPE is 4.5-fold stronger than ATPP at aggregation state.M oreover,a nu nequivocal aggregation induced electrochemiluminescence (AIECL) of ATPP-TPE was found to be seriously dependent on its aggregation property in aqueous solution with efficiency of 34 %, which is 6times higher than pure ATPP.The versatility of this molecular structure modulation strategy along with the ACQ-to-AIE transformation in this work provides direction to guide for applying liposoluble porphyrins in aqueous phase by designs of synthetic porphyrin AIEgens.