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

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

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Cyanides
cyanides
Dehydration
Ground state
electron transfer
dehydration
Electrons
ground state
Metals
Molecular electronics
X ray absorption spectroscopy
Saturation magnetization
Electronic structure
Magnetization
Atmospheric humidity
magnetization
molecular electronics
Switches
Ions
X rays

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Baker, M. L., Wu, S. Q., Kang, S., Matsuzawa, S., Arrio, M. A., Narumi, Y., ... 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

Electron-Transfer Activity in a Cyanide-Bridged Fe42 Nanomagnet. / Baker, Michael L.; Wu, Shu Qi; Kang, Soonchul; Matsuzawa, Satoshi; Arrio, Marie Anne; Narumi, Yasuo; Kihara, Takumi; Nakamura, Tetsuya; Kotani, Yoshinori; Sato, Osamu; Nojiri, Hiroyuki.

In: Inorganic Chemistry, Vol. 58, No. 15, 05.08.2019, p. 10160-10166.

Research output: Contribution to journalArticle

Baker, ML, Wu, SQ, Kang, S, Matsuzawa, S, Arrio, MA, Narumi, Y, Kihara, T, Nakamura, T, Kotani, Y, Sato, O & Nojiri, H 2019, 'Electron-Transfer Activity in a Cyanide-Bridged Fe42 Nanomagnet', Inorganic Chemistry, vol. 58, no. 15, pp. 10160-10166. https://doi.org/10.1021/acs.inorgchem.9b01216
Baker ML, Wu SQ, Kang S, Matsuzawa S, Arrio MA, Narumi Y et al. Electron-Transfer Activity in a Cyanide-Bridged Fe42 Nanomagnet. Inorganic Chemistry. 2019 Aug 5;58(15):10160-10166. https://doi.org/10.1021/acs.inorgchem.9b01216
Baker, Michael L. ; Wu, Shu Qi ; Kang, Soonchul ; Matsuzawa, Satoshi ; Arrio, Marie Anne ; Narumi, Yasuo ; Kihara, Takumi ; Nakamura, Tetsuya ; Kotani, Yoshinori ; Sato, Osamu ; Nojiri, Hiroyuki. / Electron-Transfer Activity in a Cyanide-Bridged Fe42 Nanomagnet. In: Inorganic Chemistry. 2019 ; Vol. 58, No. 15. pp. 10160-10166.
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