Controlled Synthesis of Crystalline Metalated Porphyrin Covalent Organic Frameworks through an Assembler Approach

Covalent organic frameworks (COFs) have gained a lot of attention in recent years due to their tunable porosity and functionality. Porphyrin-containing COFs have proven effective in several applications such as photo- and electrocatalysis. However, a standard reproducible procedure for the synthesis of crystalline metalated porphyrin COFs remains challenging. In this work, a general procedure using an "assembler" approach based on preorientation is reported. Octahedrally coordinating metal ions were used along with pyridinic ligands in addition to the starting monomers of the COF in a one-pot synthesis method to produce crystalline metalated porphyrin COFs with high surface area and reproducibility. Different metals, assemblers, and assembler loadings were studied, and their performances are compared. This method allows the production of high-quality porphyrin COFs which are useful for a range of applications such as catalysis, sensor technology, energy storage, and photodynamic therapy.