Electronic Effect-Modulated Enhancements of Proton Conductivity in Porous Organic Polymers

Angew Chem Int Ed Engl. 2023 Jan 9;62(2):e202214301. doi: 10.1002/anie.202214301. Epub 2022 Dec 7.

Abstract

We proposed a new strategy to maximize the density of acidic groups by modulating the electronic effects of the substituents for high-performance proton conductors. The conductivity of the sulfonated 1-MeL40-S with methyl group corresponds to 2.29×10-1 S cm-1 at 80 °C and 90 % relative humidity, remarkably an 22100-fold enhancement over the nonsulfonated 1-MeL40. 1-MeL40-S maintains long-term conductivity for one month. We confirm that this synthetic method is generalized to the extended version POPs, 2-MeL40-S and 3-MeL40-S. In particular, the conductivities of the POPs compete with those of top-level porous organic conductors. Moreover, the activation energy of the POPs is lower than that of the top-performing materials. This study demonstrates that systematic alteration of the electronic effects of substituents is a useful route to improve the conductivity and long-term durability of proton-conducting materials.

Keywords: Electronic Effect; Long-Term Performance; Porous Organic Polymers; Proton Conduction.