Transformation of an Imine Cage to a Covalent Organic Framework Film at the Liquid-Liquid Interface

Angew Chem Int Ed Engl. 2023 Jun 5;62(23):e202219083. doi: 10.1002/anie.202219083. Epub 2023 Apr 3.

Abstract

Dynamic covalent chemistry (DCC) opens up a fascinating route for the construction of well-organized supramolecular architectures, starting from organic molecular cages to crystalline macromolecular covalent organic frameworks (COFs). Herein, for the first time, we have manifested a facile room-temperature DCC-directed transformation of discrete organic imine cage-to-COF film at the liquid-liquid interface. The unfolding of the cage leading to the generation of imine intermediates, followed by their interface-assisted preorganization and subsequent growth of the COF film, are elucidated through detailed spectroscopic and microscopic investigations. The interfacial cage-to-COF transformation provides a facile route for the faster fabrication of free-standing COF films with high porosity and crystallinity, demonstrating excellent performance towards molecular sieving and high solvent permeance. Thus, the current study opens up a new route for structural interconversion between two crystalline entities with diverse dimensionality employing DCC at the confined interface.

Keywords: Covalent Organic Frameworks; Dynamic Covalent Chemistry; Interfacial Transformation; Molecular Cage; Molecular Sieving.