(90i) Solvent-Free Synthesis of Porous Organic Frameworks

Porphyrins and metalloporphyrins are known precursors to synthesize organic frameworks. It has been shown that porphyrins and metal-porphyrins can be employed as electrocatalyst for oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. There are so many other applications for these materials such as active component in optical switches, photocatalyst, separation materials, etc. Here, the focus is given to the unique feature of tetrakis(4-aminophenyl)porphyrin (TAPP) that can go through polymerization and create phenazine linkage to form a porous conjugated framework that further assemble in 3D, forming a covalent organic framework (COFs). Here, I report on the bottom-up and dry assembly of pTAPP to create 2D flakes of COF. The appearance of crystalline domains and heterostructure of pTAPP with a sub-micron length scale and the p-p stabilized superstructure was confirmed. This is the first report on a solvent-free synthetic pathway to form nanoscale crystallites.