An Approach to an Ideal Molecule-Based Mixed Conductor with Comparable Proton and Electron Conductivity
Yojiro Kimura1, Yukihiro Yoshida1, Yuki Tanaka1
1Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto 606-8502, Japan.
Abstract:
We synthesized a molecule-based proton-electron mixed conductor (PEMC), a Pt(III) dithiolate complex with 1,4-naphthoquinone skeletons. The π-planar Pt complex involves a π-stacking column, which is connected by one-dimensional hydrogen bonding chains composed of water molecules. The room-temperature (RT) proton conductivity is 8.0 × 10-5 S cm-1 under ambient conditions, which is >2 orders of magnitude higher than that of the isomorphous Ni complex (7.2 × 10-7 S cm-1). The smaller activation energy (0.23 eV) compared to that of the Ni complex (0.42 eV) possibly originates from the less dense water, which promotes the reorientational dynamics, in the Pt complex with an expanded lattice, namely, negative chemical pressure upon substitution of Ni with the larger Pt. In addition, the Pt complex shows a relatively high RT electronic conductivity of 1.0 × 10-3 S cm-1 caused by the π-columns, approaching an ideal PEMC with comparable proton and electron conduction.
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