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Ueda A, Hatakeyama A, Enomoto M, et al. Modulation of a Molecular π-Electron System in a Purely Organic Conductor that Shows Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism. Chemistry. 2015;21(42):15020-8doi: 10.1002/chem.201502047.
Ueda, A., Hatakeyama, A., Enomoto, M., Kumai, R., Murakami, Y., & Mori, H. (2015). Modulation of a Molecular π-Electron System in a Purely Organic Conductor that Shows Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism. Chemistry (Weinheim an der Bergstrasse, Germany), 21(42), 15020-8. https://doi.org/10.1002/chem.201502047
Ueda, Akira, et al. "Modulation of a Molecular π-Electron System in a Purely Organic Conductor that Shows Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 21,42 (2015): 15020-8. doi: https://doi.org/10.1002/chem.201502047
Ueda A, Hatakeyama A, Enomoto M, Kumai R, Murakami Y, Mori H. Modulation of a Molecular π-Electron System in a Purely Organic Conductor that Shows Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism. Chemistry. 2015 Oct 12;21(42):15020-8. doi: 10.1002/chem.201502047. Epub 2015 Aug 27. PMID: 26311352.
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Chemistry. 2015 Oct 12;21(42):15020-8. doi: 10.1002/chem.201502047. Epub 2015 Aug 27.

Modulation of a Molecular π-Electron System in a Purely Organic Conductor that Shows Hydrogen-Bond-Dynamics-Based Switching of Conductivity and Magnetism.

Chemistry (Weinheim an der Bergstrasse, Germany)

Akira Ueda, Akari Hatakeyama, Masaya Enomoto, Reiji Kumai, Youichi Murakami, Hatsumi Mori

Affiliations

  1. The Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581 (Japan). [email protected].
  2. The Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581 (Japan).
  3. Department of Chemistry, Faculty of Science Division I, Tokyo University of Science, Shinjuku-ku, Tokyo 162-8601 (Japan).
  4. Condensed Matter Research Center (CMRC) and Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Tsukuba, Ibaraki 305-0801 (Japan).
  5. The Institute for Solid State Physics, The University of Tokyo, Kashiwa, Chiba 277-8581 (Japan). [email protected].

PMID: 26311352 DOI: 10.1002/chem.201502047

Abstract

New important aspects of the hydrogen-bond (H-bond)-dynamics-based switching of electrical conductivity and magnetism in an H-bonded, purely organic conductor crystal have been discovered by modulating its tetrathiafulvalene (TTF)-based molecular π-electron system by means of partial sulfur/selenium substitution. The prepared selenium analogue also showed a similar type of phase transition, induced by H-bonded deuterium transfer followed by electron transfer between the H-bonded TTF skeletons, and the resulting switching of the physical properties; however, subtle but critical differences due to sulfur/selenium substitution were detected in the electronic structure, phase transition nature, and switching function. A molecular-level discussion based on the crystal structures shows that this chemical modification of the TTF skeleton influences not only its own π-electronic structure and π-π interactions within the conducting layer, but also the H-bond dynamics between the TTF π skeletons in the neighboring layers, which enables modulation of the interplay between the H-bond and π electrons to cause such differences.

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: conducting materials; electron transfer; hydrogen bonds; hydrogen transfer; phase transitions

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