Programmable Electronic Communication in Covalent Organic Frameworks Enabled by Multicomponent Assembly for Enhanced...

Efficient donor-acceptor (D-A) electronic coupling is critical for optimizing charge transport in covalent organic frameworks (COFs). However, linkage-induced spatial segregation in conventional binary COFs disrupts carrier continuity, thereby severely limiting electrochemiluminescence (ECL), a process that demands rapid, synchronized, and directional charge dynamics. To overcome this constraint, we develop a rationally designed multicomponent assembly strategy based on orthogonal Betti and Scholl reactions, enabling stepwise enhancement of through-bond electronic connectivity. Specifically, the strategic incorporation of a phenolic third component bridges spatially isolated donor and acceptor units, establishing uninterrupted intramolecular charge-transport pathways and yielding a 24.4-fold increase in ECL intensity relative to the binary analogue. Furthermore, the synergistic action of Betti and Scholl reactions drives in situ cyclization to form rigid, planar tetrahydroquinoline linkages, thereby improving backbone coplanarity, extending π-conjugation across the D-A interface, and amplifying ECL emission by 3.7-fold compared with the ternary precursor. Crucially, selective disruption of these extended π-pathways via coordination with UO₂ ²⁺ ions induces quantifiable, dose-dependent ECL quenching, providing direct experimental evidence of a structure-function relationship between multicomponent-engineered electronic connectivity and signal transduction. This work establishes a mechanism for how multicomponent assembly controls topological electronic connectivity in COFs, providing a general design principle to tailor charge transport in functional materials.