Ionic Covalent–Organic Frameworks Composed of Anthryl-Extended Viologen as a Kind of Electrochemiluminescence Luminophore

Nowadays, covalent-organic frameworks (COFs) integrated with the electrochemiluminescence (ECL) behavior are highly desired owing to the significant advantages including multifunctionality, high sensitivity, and low background noise. Here, two ionic COFs (iCOFs) consisting of the anthryl-extended viologen as the backbone were designed and synthesized via the Zincke reaction. It is found for the first time that the as-prepared iCOFs accompanied by potassium persulfate as the coreactant can provide a clear ECL response in a water-bearing medium. The maximum ECL emissions of the iCOFs were in agreement with the photoluminescence spectra. Besides, cyclic voltammetry and electron paramagnetic resonance measurements reveal that the pyridinium unit was electrochemically reduced to afford the free radical. Then, it reacted with SO₄^·- to generate the excited-state [iCOF]*. Finally, [iCOF]* quickly returned to its ground state coupled with a clear ECL emission, yielding a maximum ECL quantum efficiency of 23.4% compared with tris(2,2'-bipyridyl) ruthenium(II) as the benchmark. In brief, the current study opens a way to develop a kind of ECL emitter that holds great potential in sensing, imaging, and light-emitting devices.