Covalent Organic Frameworks with 2-Fold Functional Pores Produced from a Monofunctional Monomer as Predicted by Computational Methods

Manipulating pore groups in covalent organic frameworks (COFs) changes the function of the material while also modifying pore size. These groups are often assumed based on monomer structure; however, common characterization techniques can be inadequate in the verification of these pore groups. Computational modeling has the ability to predict and illustrate the potential errors that may arise within these COF structures. We report herein a side reaction in two synthesized COFs that was identified through simulation data and confirmed through a variety of techniques. The synthetic conditions and mechanistic rationale leading to this side reaction can be rationalized with the use of computational insight, which proves to be a powerful tool in providing insight into these polymeric materials. As a result, a COF with two different functional groups within the pore has been constructed from a monofunctionalized monomer.