Electroactive Metal–Organic Frameworks as Emitters for Self‐Enhanced Electrochemiluminescence in Aqueous Medium

Metal-organic frameworks (MOFs) have limited applications in electrochemistry owing to their poor conductivity. Now, an electroactive MOF (E-MOF) is designed as a highly crystallized electrochemiluminescence (ECL) emitter in aqueous medium. The E-MOF contains mixed ligands of hydroquinone and phenanthroline as oxidative and reductive couples, respectively. E-MOFs demonstrate excellent performance with surface state model in both co-reactant and annihilation ECL in aqueous medium. Compared with the individual components, E-MOFs significantly improve the ECL emission due to the framework structure. The self-enhanced ECL emission with high stability is realized by the accumulation of MOF cation radicals via pre-reduction electrolysis. The self-enhanced mechanism is theoretically identified by DFT. The mixed-ligand E-MOFs provide a proof of concept using molecular crystalline materials as new ECL emitters for fundamental mechanism studies.