1e:T55c,This work presents a mixed-ligand metal-organic framework (m-MOF) integrated with two ligands, one as a luminophore and the other as a coreactant, on one metal node for self-enhanced electrochemiluminescence (ECL). Both 9,10-di(p-carboxyphenyl)anthracene (DPA) and 1,4-diazabicyclo[2.2.2]octane (D-H₂) ligands can be oxidized, generating the cation radicals DPA^+• and D-H₂^+•, respectively. The latter can be deprotonated to form the neutral radical (D-H^•) and then react with DPA^+• to produce excited DPA* for ECL emission without exogenous coreactants. As a result of the incorporation into the MOF framework and the intrareticular charge transfer between the two ligands, the ECL intensity of the m-MOF was increased 26.5-fold compared with that of the mixture of DPA and D-H₂ in aqueous solution. Moreover, with the process of second oxidation of D-H₂, stepwise ECL emission was observed as a result of local excitation in the DPA unit, which was identified through density functional theory calculations. Overall, the implementation of the mixed-ligand approach, which combines the luminophore and coreactant as linkers in reticular materials, enriches the fundamentals and applications of ECL systems.1f:T45a,A bio-coreactant-enhanced electrochemiluminescence (ECL) microscopy realizes the ECL imaging of intracellular structure and dynamic transport. This microscopy uses Ru(bpy)₃²⁺ as the electrochemical molecular antenna connecting extracellular and intracellular environments, and uses intracellular biomolecules as the coreactants of ECL reactions via a "catalytic route". Accordingly, intracellular structures are identified without using multiple labels, and autophagy involving DNA oxidative damage is detected using nuclear ECL signals. A time-resolved image sequence discloses the universal edge effect of cellular electroporation due to the influence of the geometric properties of cell membranes on the induced transmembrane voltage. The dynamic transport of Ru(bpy)₃³⁺ in the different cellular compartments unveils the heterogeneous intracellular diffusivity correlating with the actin cytoskeleton. In addition to single-cell studies, the bio-coreactant-enhanced ECL microscopy is used to image a slice of a mouse liver and a colony of Shewanella oneidensis MR-1.20:T599,

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