Supramolecular Proton Conductors Self-Assembled by Organic Cages

Proton conduction is vital for living systems to execute various physiological activities. The understanding of its mechanism is also essential for the development of state-of-the-art applications, including fuel-cell technology. We herein present a bottom-up strategy, that is, the self-assembly of Cage-1 and -2 with an identical chemical composition but distinct structural features to provide two different supramolecular conductors that are ideal for the mechanistic study. Cage-1 with a larger cavity size and more H-bonding anchors self-assembled into a crystalline phase with more proton hopping pathways formed by H-bonding networks, where the proton conduction proceeded via the Grotthuss mechanism. Small cavity-sized Cage-2 with less H-bonding anchors formed the crystalline phase with loose channels filled with discrete H-bonding clusters, therefore allowing for the translational diffusion of protons, that is, vehicle mechanism. As a result, the former exhibited a proton conductivity of 1.59 × 10^-4 S/cm at 303 K under a relative humidity of 48%, approximately 200-fold higher compared to that of the latter. Ab initio molecular dynamics simulations revealed distinct H-bonding dynamics in Cage-1 and -2, which provided further insights into potential proton diffusion mechanisms. This work therefore provides valuable guidelines for the rational design and search of novel proton-conducting materials.