An organic proton cage that is ultra-resistant to hydroxide-promoted degradation.

Alkaline polymer membrane electrochemical energy conversion devices offer the prospect of using non-platinum group catalysts. However, their cationic functionalities are currently not sufficiently stable for vapor-phase applications, such as fuel cells. Herein, we report 1,6-diazabicyclo[4.4.4]tetradecan-1,6-ium (in-DBD), a cationic proton cage, that is orders of magnitude more resistant to hydroxide-promoted degradation than state-of-the-art organic cations under ultra-dry conditions and elevated temperature, and the first organic cation-hydroxide to persist at critically low hydration levels ( < 10% RH at 80 °C). This high stability against hydroxide-promoted degradation is due to the unique combination of endohedral protection and intra-bridgehead hydrogen bonding that prevents the removal of the inter-cavity proton and lowers the susceptibility to Hofmann elimination. We anticipate this discovery will facilitate a step-change in the advancement of materials and electrochemical devices utilizing anion-exchange membranes based on in-DBD that will enable stable operation under extreme alkaline conditions.