Facile one-pot synthesis of mulberry-shape silver nanoparticle-doped porphyrin nanoassembly with self-promoted electrochemiluminescence

The electrochemiluminescence (ECL) efficiency of porphyrins is limited by the quenching of pi-pi stacking due to their poor water solubility and inherent instability. Therefore, there is an urgent need to design and explore novel porphyrin luminophores with high ECL efficiency, which presents a significant challenge. In this work, a facile one-pot strategy was developed to synthesize a self-promoter-doped porphyrin-based ECL luminophore with high ECL efficiency for the first time. The silver nanoparticle (AgNPs)-doped meso-tetra(4-carboxyphenyl) porphyrin (TCPP) (AgNPs@TCPP) nanoassembly was prepared by inducing TCPP assembly using Ag nanoseeds produced by the reduction of silver nitrate with N,N-dimethylformamide. In this process, AgNPs could coordinate with the carboxyphenyl groups at the terminus of TCPP and the pyrrole nitrogen of TCPP. The resulting AgNPs@TCPP nanoassembly demonstrated superior ECL performance using K2S2O8 as a co-reactant, with an ECL efficiency of 217%, significantly higher than that of previously reported sodium dodecyl sulfate-assisted TCPP aggregate (92.3%) and cetyltrimethylammonium bromide-assisted TCPP aggregate (57.5%). The self-promoted and highly efficient ECL of the AgNPs@TCPP nanoassembly was attributed to overcoming the ECL quenching due to bad TCPP aggregation by virtue of Ag nanoseeds induced TCPP assembly and the self-promoted ECL amplification by doping AgNPs with excellent conductivity. These findings offer a new approach for exploring highly efficient porphyrin-based ECL luminophores, thereby expanding the applications of porphyrins in ECL. Mulberry-shape silver nanoparticle-doped porphyrin nanoassembly with self-promoted high efficiency electrochemiluminescence was synthesized by a facile one-pot strategy.