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

Area of Science:

• Materials Science
• Organic Chemistry
• Electrochemistry

Background:

• Efficient donor-acceptor (D-A) electronic coupling is crucial for charge transport in covalent organic frameworks (COFs).
• Spatial segregation in conventional binary COFs limits electrochemiluminescence (ECL) due to disrupted carrier continuity.
• Rapid, synchronized, and directional charge dynamics are essential for optimal ECL performance.

Purpose of the Study:

• To develop a multicomponent assembly strategy for enhancing through-bond electronic connectivity in COFs.
• To improve charge transport and electrochemiluminescence (ECL) efficiency in COFs.
• To establish a structure-function relationship between electronic connectivity and signal transduction in COFs.

Main Methods:

• Utilized orthogonal Betti and Scholl reactions for stepwise enhancement of electronic connectivity.
• Incorporated a phenolic third component to bridge spatially isolated donor and acceptor units.
• Investigated the effect of UO2^2+ ion coordination on ECL quenching to demonstrate structure-function relationships.

Main Results:

• Achieved a 24.4-fold increase in ECL intensity compared to binary COFs by bridging D-A units.
• Synergistic reactions formed rigid, planar tetrahydroquinoline linkages, amplifying ECL emission by 3.7-fold.
• Demonstrated dose-dependent ECL quenching upon UO2^2+ coordination, confirming engineered electronic connectivity.

Conclusions:

• Multicomponent assembly strategy effectively enhances intramolecular charge-transport pathways in COFs.
• Rigid, planar linkages improve backbone coplanarity and extend π-conjugation, boosting ECL.
• This work provides a general design principle for tailoring charge transport and signal transduction in functional materials via controlled electronic connectivity.