The influence of disorder in the synthesis, characterization and applications of a modifiable two‐dimensional covalent organic framework

Abstract

Two‐dimensional covalent organic frameworks (2D‐COFs) have been of increasing interest in the past decade due to their porous structures that ideally can be highly ordered. One of the most common routes to these polymers relies on Schiff‐base chemistry, i.e., the condensation reaction between a carbonyl and an amine. In this report, we elaborate on the condensation of 3,6‐ dibromobenzene‐1,2,4,5‐tetraamine with hexaketocyclohexane (HKH) and the subsequent carbonylation of the resulting COF, along with the possibility that the condensation reaction on HKH can result in a trans configuration resulting in the formation of a disordered 2D‐COF. This strategy enables modification of COFs via bromine substitution reactions to place functional groups within the pores of the materials. Ion‐sieving measurements using membranes from this COF, reaction of small molecules with unreacted keto groups along with modeling studies indicate disorder in the COF polymerization process. We also present a Monte Carlo simulation that demonstrates the influence of even small amounts of disorder upon both the 2D and 3D structure of the resulting COF.