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Recent Progress in Stable High-Spin Molecules Based on Nitroxide Radicals

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Book cover Chemical Science of π-Electron Systems

Abstract

Organic-based open-shell π-electronic molecules are promising components for unique electronic devices because of the diversity in their design. Of these compounds, high-spin π-electronic molecules are attractive building blocks of molecule-based magnets and spintronic devices. However, there are only a few reports of high-spin π-electronic molecules with large intramolecular exchange interactions (J intra/k B > + 300 K) and with isolable stability, although general guides of molecular designs to obtain high-spin π-electronic molecules have already been established. In this chapter, recent studies from our research group on high-spin π-electronic molecules are reported. First, stable trimethylenemethane analogues composed of nitroxide and nitronyl nitroxide or imino nitroxide moieties and their metal complexes are outlined. This is followed by the description of (nitronyl nitroxide)-substituted electron donor radical cations as new components for molecule-based magnets. Finally, a trinitroxide-substituted trioxytriphenylamine is discussed, which constitutes a novel spin-state conversion system.

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Acknowledgments

These works were partially supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Emergence of Highly Elaborated π-Space,” “Stimuli-Responsive Chemical Species for the Creation of Functional Molecules,” and “π-System Figuration: Control of Electron and Structural Dynamism for Innovative Functions” from MEXT.

The author gratefully acknowledges the invaluable discussions, many helpful suggestions, and encouragement of Professor Keiji Okada and Associate Professor Masatoshi Kozaki. The author would like to thank Professor Takeji Takui, Professor Kazunobu Sato, Associate Professor Daisuke Shiomi, Dr. Kazuo Toyota, and Dr. Kenji Sugisaki (Osaka City University) for their ESR and SQUID measurements, theoretical calculations, and helpful discussions. The author would also like to thank Professor Yuko Hosokoshi (Osaka Prefecture University) for SQUID measurements and Associate Professor Yuji Miyazaki and Professor Akira Inaba (Osaka University) for their heat capacity measurements.

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Authors and Affiliations

  1. Department of Chemistry, Graduate School of Science, Osaka City University, Osaka, Japan

    Shuichi Suzuki

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  1. Shuichi Suzuki
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Correspondence to Shuichi Suzuki .

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Editors and Affiliations

  1. Foundation for Advancement of International Science, Tsukuba, Japan

    Takeshi Akasaka

  2. Kyoto University, Kyoto, Japan

    Atsuhiro Osuka

  3. Department of Chemistry and Nano Science,, Ewha Womans University, Seoul, Korea (Republic of)

    Shunichi Fukuzumi

  4. Nagoya Institute of Technology, Nagoya, Japan

    Hideki Kandori

  5. Osaka University, Suita, Japan

    Yoshio Aso

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Suzuki, S. (2015). Recent Progress in Stable High-Spin Molecules Based on Nitroxide Radicals. In: Akasaka, T., Osuka, A., Fukuzumi, S., Kandori, H., Aso, Y. (eds) Chemical Science of π-Electron Systems. Springer, Tokyo. https://doi.org/10.1007/978-4-431-55357-1_19

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