Porphyrins and their derivatives have attracted many researchers’ attention as they are precursors for the preparation of covalent organic frameworks (COFs). It has been demonstrated that porphyrin and its metal complexes can be employed as electrocatalysts, especially for oxygen reduction and carbon dioxide reduction reactions. In addition to this, these applications of materials have also been explored in photocatalysis, separation, optical switches and so on. Polymerization of porphyrins to create frameworks and networks increases the stability of these materials, thus preparing porphyrins-based COFs are important to their widespread applications. COFs are commonly synthesized via solvothermal method, which involves with very long reaction time and usage of toxic organic solvents. Thus, the design of a synthetic dry pathway is highly desirable. In addition, from a production standpoint, the development of an environmentally friendly, facile and green synthetic pathway for the synthesis of COFs is advantageous. Herein, we report the one-step, solvent-free synthesis of crystalline and porous porphyrin-based COFs. Both of 5,10,15,20-tetra(4-aminophenyl)porphyrin (TAPP) or its transition metal complex (MPOR-COF, M = H2, Cu, Co, Zn) in the presence of antimony pentachloride (SbCl5), as a Lewis acid, polymerized. The monomer TAPP undergoes polymerization via phenazine link formation (pTAPP) in the presence of SbCl5 and led to the formation of well-ordered MPOR-COFs. Here, we report on the bottom-up and dry assembly of pTAPP and their derivatives to create active materials. We also report on the control we achieved on the reaction selectivity and separation performance of the thin films deposited through the oxidative vapor phase polymerization pathway and explore various strategies to control the film structure and properties.

Synthesis of porphyrin-based two-dimensional covalent organic frameworks via oxidative molecular layer deposition

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