Covalent Organic Frameworks with 2‑Fold Functional Pores Produced from a Monofunctional Monomer as Predicted by...

Area of Science:

• Materials Science
• Polymer Chemistry
• Computational Chemistry

Background:

• Covalent organic frameworks (COFs) are tunable porous materials whose function is dictated by pore chemistry.
• Characterizing functional groups within COF pores is challenging with standard techniques.
• Accurate structural verification is crucial for predictable COF material properties.

Purpose of the Study:

• To investigate potential discrepancies between assumed and actual pore group structures in synthesized COFs.
• To demonstrate the utility of computational modeling in identifying synthetic side reactions.
• To report the successful synthesis of a COF with dual functional groups from a monofunctionalized monomer.

Main Methods:

• Computational modeling (e.g., simulations) to predict structural anomalies.
• Synthesis of two specific COF materials.
• Verification of simulated findings using various experimental characterization techniques.

Main Results:

• A previously unidentified side reaction occurring during COF synthesis was discovered via simulation data.
• This side reaction was experimentally confirmed using multiple characterization methods.
• Computational insights elucidated the mechanistic pathway and synthetic conditions leading to the side reaction.

Conclusions:

• Computational modeling is a powerful tool for understanding and troubleshooting COF synthesis.
• It provides critical insights into polymeric material structures that may be missed by traditional characterization.
• This work led to the successful construction of a COF with two distinct pore functional groups derived from a single monomer precursor.