A Preinstalled Protic Cation as a Switch for Superprotonic Conduction in a Metal–Organic Framework

[Image: see text] Metal–organic frameworks (MOFs), made from various metal nodes and organic linkers, provide diverse research platforms for proton conduction. Here, we report on the superprotonic conduction of a Pt dimer based MOF, [Pt(2)(MPC)(4)Cl(2)Co(DMA)(HDMA)·guest] (H(2)MPC, 6-mercaptopyridine-3-carboxylic acid; DMA, dimethylamine). In this framework, a protic dimethylammonium cation (HDMA(+)) is trapped inside a pore through hydrogen bonding with an MPC ligand. Proton conductivity and X-ray measurements revealed that trapped HDMA(+) works as a preinstalled switch, where HDMA(+) changes its relative position and forms an effective proton-conducting pathway upon hydration, resulting in more than 10(5) times higher proton conductivity in comparison to that of the dehydrated form. Moreover, the anisotropy of single-crystal proton conductivity reveals the proton-conducting direction within the crystal. The present results offer insights into functional materials having a strong coupling of molecular dynamic motion and transport properties.