Templating Method for Preparing Functionalized Polymers of Intrinsic Microporosity with Versatile Potential

Functionalized polymers of intrinsic microporosity (PIMs) have been widely employed in gas separation, ion conduction, and energy storage. However, it is difficult to develop a universal method to functionalize PIMs for a variety of movable particles. Herein, template PIMs bearing highly reactive benzyl bromides were synthesized and functionalized to carry four types of movable particles, including cations, anions, radicals, and deformable moieties, showing versatile potential. The ideal CO2/N2 selectivity of functionalized PIMs was carried out to reveal the unique interactions between functionalized groups and gas molecules. Ionic and radical characteristics of functionalized PIMs were demonstrated. Azobenzene-functionalized PIMs were used as solar thermal fuels, showing a high storage energy density of 120.3 J g–1 and a storage enthalpy of 192.8 kJ mol–1, which are higher than those of the parent molecule and previously reported polymer-based solar thermal fuels. This work provides a universal approach to preparing functionalized PIMs and demonstrates their versatile potential.