Volume 63, Issue 14 e202400162
Communication

A Three-Dimensionally Extended Metal–Organic Ladder Compound Exhibiting Proton Conduction

Hao Liang

Hao Liang

Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto, 606-8502 Japan

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Dr. Kazuya Otsubo

Corresponding Author

Dr. Kazuya Otsubo

Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto, 606-8502 Japan

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Prof. Dr. Yusuke Wakabayashi

Prof. Dr. Yusuke Wakabayashi

Department of Physics, Tohoku University, Sendai, 980-8578 Japan

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Dr. Hajime Sagayama

Dr. Hajime Sagayama

Institute of Materials Structure Science, High Energy Accelerator Research Organization, Tsukuba, 305-0801 Japan

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Dr. Shogo Kawaguchi

Dr. Shogo Kawaguchi

Japan Synchrotron Radiation Research Institute (JASRI), SPring-8, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo, 679-5198 Japan

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Prof. Dr. Hiroshi Kitagawa

Corresponding Author

Prof. Dr. Hiroshi Kitagawa

Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto, 606-8502 Japan

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First published: 09 February 2024
Citations: 5

Graphical Abstract

The synthesis of a three-dimensionally (3D) extended two-legged ladder compound was reported for the first time. The unique 3D extended lattice consists of one-dimensional (1D) mixed-valence halogen-bridged metal chains (⋅⋅⋅Pt−I−Pt−I⋅⋅⋅) and helically arranged macrocyclic units as the constituent legs and rungs. The out-of-phase mixed-valence Pt2+/Pt4+ arrangement arises from the weak interchain correlation among adjacent legs.

Abstract

Ladder systems situated in the dimensional crossover region have attracted much attention because their electronic states and physical properties depend strongly on the electronic correlations among the constituent legs. Generally, two-/three-legged transition metal-oxide ladder compounds are studied as representative ladder systems, but two-/three-dimensional (2D/3D) extensions based on such ladder systems with a few numbers of legs are difficult because of the extreme synthesis conditions. Here, for the first time, we report the successful creation of a 3D extended two-legged ladder compound, [Pt(en)(dpye)I]2(NO3)4 ⋅ 2H2O (en=ethylenediamine; dpye=1,2-Di(4-pyridyl)ethane), which is obtained by simple oxidative polymerization of a small Pt macrocyclic complex using elemental I2. The unique 3D extended lattice consists of 1D mixed-valence halogen-bridged metal chains (⋅⋅⋅Pt−I−Pt−I⋅⋅⋅) and helically arranged macrocyclic units as the constituent legs and rungs, as confirmed by single-crystal X-ray diffraction. Diffuse X-ray scattering analyses and optical measurements revealed that the out-of-phase mixed-valence Pt2+/Pt4+ arrangement arises from the weak interchain correlation among adjacent legs. In addition, this compound shows an increase in proton conductivity by a factor of up to 1000, depending on humidity.

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

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