Metal

Adsorption

Electrochemiluminescence

Electrochemistry

Photochemistry

Materials science

Hydroquinone

Receptor

Biochemistry

Inorganic chemistry

Physical chemistry

Cathodic protection

Combinatorial chemistry

Ligand (biochemistry)

Nanotechnology

Organic chemistry

Aqueous solution

Metal-organic framework

Radical

Chemistry

Electrode

Aqueous medium

Electrolyte

Electrolysis

Angewandte Chemie International Edition

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.

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