Electron-Transfer Activity in a Cyanide-Bridged Fe42 Nanomagnet

Michael L. Baker, Shu Qi Wu, Soonchul Kang, Satoshi Matsuzawa, Marie Anne Arrio, Yasuo Narumi, Takumi Kihara, Tetsuya Nakamura, Yoshinori Kotani, Osamu Sato, Hiroyuki Nojiri

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The ability to switch a molecule between different magnetic states is of considerable importance for the development of new molecular electronic devices. Desirable properties for such applications include a large-spin ground state with an electronic structure that can be controlled via external stimuli. Fe42 is a cyanide-bridged stellated cuboctahedron of mixed-valence Fe ions that exhibits an extraordinarily large S = 45 spin ground state. We have found that the spin ground state of Fe42 can be altered by controlling the humidity and temperature. Dehydration results in a 15 μB reduction of the saturation magnetization that can be partially recovered upon rehydration. The complementary use of UV-vis, IR, L2,3-edge X-ray absorption spectroscopy and X-ray magnetic circular dichroism is applied to uncover the mechanism for the observed dynamic behavior. It is identified that dehydration is concurrent with metal-to-metal electron transfer between Fe pairs via a cyanide πhybridization. Upon dehydration, electron transfer occurs from low-spin {FeII(Tp)(CN)3} sites to high-spin FeIII centers. The observed reduction in magnetization upon dehydration of Fe42 is inconsistent with a ferrimagnetic ground state and is proposed to originate from a change in zero-field splitting at electron-reduced high-spin sites.

Original languageEnglish
Pages (from-to)10160-10166
Number of pages7
JournalInorganic chemistry
Volume58
Issue number15
DOIs
Publication statusPublished - Aug 5 2019

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Electron-Transfer Activity in a Cyanide-Bridged Fe<sub>42</sub> Nanomagnet'. Together they form a unique fingerprint.

  • Cite this

    Baker, M. L., Wu, S. Q., Kang, S., Matsuzawa, S., Arrio, M. A., Narumi, Y., Kihara, T., Nakamura, T., Kotani, Y., Sato, O., & Nojiri, H. (2019). Electron-Transfer Activity in a Cyanide-Bridged Fe42 Nanomagnet. Inorganic chemistry, 58(15), 10160-10166. https://doi.org/10.1021/acs.inorgchem.9b01216