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Chemically Stable Carbazole-Based Imine Covalent Organic Frameworks with Acidochromic Response for Humidity Control Applications

Year: 2021

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide Isoreticular chemically stable two-dimensional imine covalent organic frameworks (COFs), further denoted as DUT-175 and DUT-176, are obtained in a reaction of 4,4′-bis(9 H -carbazol-9-yl)biphenyl tetraaldehyde with phenyldiamine and benzidine. The crystal structures, solved and refined from the powder X-ray diffraction data and confirmed by high-resolution transmission electron microscopy, indicate AA-stacked layer structures. Both structures feature distorted hexagonal channel pores, assuring remarkable porosity ( S BET = 1071 m 2 g –1 for DUT-175 and S BET = 1062 m 2 g –1 for DUT-176), as confirmed by adsorption of gases and vapors. The complex conjugated π system of the COFs involves electron-rich carbazole building units, which in combination with the imine groups allow reversible pH-dependent protonation of the frameworks, accompanied by charge transfer and shift of the absorption bands in the UV–vis spectrum. The sigmoidal shape of the water vapor adsorption and desorption isotherms with a steep adsorption step at p / p 0 = 0.4–0.6 in combination with excellent stability over dozens of adsorption and desorption cycles ranks these COFs among the best materials for indoor humidity control applications.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.1c07148