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Download fileA Preinstalled Protic Cation as a Switch for Superprotonic Conduction in a Metal–Organic Framework
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posted on 04.01.2022, 01:04 authored by Kazuya Otsubo, Shuya Nagayama, Shogo Kawaguchi, Kunihisa Sugimoto, Hiroshi KitagawaMetal–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, [Pt2(MPC)4Cl2Co(DMA)(HDMA)·guest] (H2MPC, 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 105 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.
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various metal nodesray measurements revealedprotic dimethylammonium cationmolecular dynamic motionmofs ), madeconducting direction withinpreinstalled protic cation5 </ sup4 </ sub2 </ subsup >+</ suptrapped insidetransport propertiessuperprotonic conductionstrong couplingrelative positionpreinstalled switchorganic linkershydrogen bondingfunctional materialsdimethylamine ).dehydrated formcarboxylic acid