Electrical Network of Single-Crystalline Metal Oxide Nanoclusters Wired by π-Molecules

• Published in: Angewandte Chemie (International ed.) Vol. 53; no. 42; pp. 11228 - 11231
• Main Authors: Tsunashima, Ryo, Iwamoto, Yoshifumi, Baba, Yusuke, Kato, Chisato, Ichihashi, Katsuya, Nishihara, Sadafumi, Inoue, Katsuya, Ishiguro, Katsuya, Song, Yu-Fei, Akutagawa, Tomoyuki
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 13.10.2014; WILEY‐VCH Verlag
• Subjects: Acetal resins; Anions; Cationic; Clusters; conducting materials; Electric wire; Electrical properties; Low level; Metal oxides; molecular electronics; nanoparticles; polyoxometalates; Single crystals; conducting materials; molecular electronics; nanoparticles; polyoxometalates
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201406223

In a mixed‐valence polyoxometalate, electrons are usually delocalized within the cluster anion because of low level of inter‐cluster interaction. Herein, we report the structure and electrical properties of a single crystal in which mixed‐valence polyoxometalates were electrically wired by cationic π‐molecules of tetrathiafulvalene substituted with pyridinium. Electron‐transport characteristics are suggested to represent electron hopping through strong interactions between cluster and cationic π‐molecules. Down to the wire: In a mixed‐valence polyoxometalate (POM), electrons are usually delocalized within the metal cluster anion because of a low degree of inter‐cluster interaction. If the mixed‐valence POMs are electrically linked together by wires of cationic π molecules of tetrathiafulvalene substituted with pyridinium, electron transport can occur by electron hopping as a result of the strong interactions between cluster and cationic π molecules.