Fine‐Tunable Electronic Energy Levels of Mixed‐Metal Prussian‐Blue Alloy Nanoparticles

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  • Manabu Ishizaki
    Department of Material and Biological Chemistry Yamagata University 1-4-12 Kojirakawa-machi Yamagata 990-8560 Japan
  • Kenta Ono
    Department of Material and Biological Chemistry Yamagata University 1-4-12 Kojirakawa-machi Yamagata 990-8560 Japan
  • Kento Suzuki
    Department of Material and Biological Chemistry Yamagata University 1-4-12 Kojirakawa-machi Yamagata 990-8560 Japan
  • Wataru Naito
    Department of Material and Biological Chemistry Yamagata University 1-4-12 Kojirakawa-machi Yamagata 990-8560 Japan
  • Katsuhiko Kanaizuka
    Department of Material and Biological Chemistry Yamagata University 1-4-12 Kojirakawa-machi Yamagata 990-8560 Japan
  • Tohru Kawamoto
    Nanomaterials Research Institute National Institute of Advanced Industrial Science and Technology (AIST) 1-1-1 Higashi Tsukuba 305-8565 Japan
  • Hisashi Tanaka
    Nanomaterials Research Institute National Institute of Advanced Industrial Science and Technology (AIST) 1-1-1 Higashi Tsukuba 305-8565 Japan
  • Masato Kurihara
    Department of Material and Biological Chemistry Yamagata University 1-4-12 Kojirakawa-machi Yamagata 990-8560 Japan

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<jats:title>Abstract</jats:title><jats:p>A specific electronic interaction among metal ions emerges in solution‐processed films of coordination polymer (CP) nanoparticles (NPs). The most classic CP, Prussian blue (PB), is alloyed with Ni to form Fe<jats:sub><jats:italic>x</jats:italic></jats:sub>Ni<jats:sub>3−<jats:italic>x</jats:italic></jats:sub>[Fe(CN)<jats:sub>6</jats:sub>]<jats:sub>2</jats:sub> showing an identical X‐ray crystallographic phase in all composition ratios of 0≤<jats:italic>x</jats:italic>≤3. By surface modification using [Fe(CN)<jats:sub>6</jats:sub>]<jats:sup>4−</jats:sup>, the PB alloy NPs are dispersed into water, and spin‐coated films of the NPs adhere to indium‐tin‐oxide substrates via a low‐temperature heating process at 100 °C. It is revealed that systematic fine tuning of the electronic energy levels is optically and electrochemically possible in the films by controlling the composition ratios. This is possible due to the <jats:italic>d</jats:italic>(<jats:italic>t</jats:italic><jats:sub>2g</jats:sub>)–<jats:italic>π</jats:italic>*(C≡N<jats:sup>−</jats:sup>) electronic conjugation among three redox‐active iron species, Fe<jats:sup>II</jats:sup>−C≡N, Fe<jats:sup>III</jats:sup>−C≡N, and Fe<jats:sup>III</jats:sup>−N≡C, which coexist by alloying with Ni. The heating process conducts the restoration of discontinued d–π* bonding networks among the NPs.</jats:p>

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  • ChemNanoMat

    ChemNanoMat 3 (5), 288-291, 2017-04-20

    Wiley

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