Temperature dependence of spherical electron transfer in a nanosized [Fe14] complex

Wei Huang; Shuqi Wu; Xiangwei Gu; Yao Li; Atsushi Okazawa; Norimichi Kojima; Shinya Hayami; Michael L. Baker; Peter Bencok; Mariko Noguchi; Yuji Miyazaki; Motohiro Nakano; Takumi Nakanishi; Shinji Kanegawa; Yuji Inagaki; Tatsuya Kawae; Gui Lin Zhuang; Yoshihito Shiota; Kazunari Yoshizawa; Dayu Wu; Osamu Sato

doi:10.1038/s41467-019-13279-y

Temperature dependence of spherical electron transfer in a nanosized [Fe₁₄] complex

Wei Huang, Shuqi Wu, Xiangwei Gu, Yao Li, Atsushi Okazawa, Norimichi Kojima, Shinya Hayami, Michael L. Baker, Peter Bencok, Mariko Noguchi, Yuji Miyazaki, Motohiro Nakano, Takumi Nakanishi, Shinji Kanegawa, Yuji Inagaki, Tatsuya Kawae, Gui Lin Zhuang, Yoshihito Shiota, Kazunari Yoshizawa, Dayu WuOsamu Sato

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Abstract

The study of transition metal clusters exhibiting fast electron hopping or delocalization remains challenging, because intermetallic communications mediated through bridging ligands are normally weak. Herein, we report the synthesis of a nanosized complex, [Fe(Tp)(CN)₃]₈[Fe(H₂O)(DMSO)]₆ (abbreviated as [Fe₁₄], Tp⁻, hydrotris(pyrazolyl)borate; DMSO, dimethyl sulfoxide), which has a fluctuating valence due to two mobile d-electrons in its atomic layer shell. The rate of electron transfer of [Fe₁₄] complex demonstrates the Arrhenius-type temperature dependence in the nanosized spheric surface, wherein high-spin centers are ferromagnetically coupled, producing an S = 14 ground state. The electron-hopping rate at room temperature is faster than the time scale of Mössbauer measurements (<~10⁻⁸ s). Partial reduction of N-terminal high spin Fe^III sites and electron mediation ability of CN ligands lead to the observation of both an extensive electron transfer and magnetic coupling properties in a precisely atomic layered shell structure of a nanosized [Fe₁₄] complex.

Original language	English
Article number	5510
Journal	Nature communications
Volume	10
Issue number	1
DOIs	https://doi.org/10.1038/s41467-019-13279-y
Publication status	Published - Dec 1 2019

All Science Journal Classification (ASJC) codes

Chemistry(all)
Biochemistry, Genetics and Molecular Biology(all)
Physics and Astronomy(all)

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10.1038/s41467-019-13279-y

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Huang, W., Wu, S., Gu, X., Li, Y., Okazawa, A., Kojima, N., Hayami, S., Baker, M. L., Bencok, P., Noguchi, M., Miyazaki, Y., Nakano, M., Nakanishi, T., Kanegawa, S., Inagaki, Y., Kawae, T., Zhuang, G. L., Shiota, Y., Yoshizawa, K., ... Sato, O. (2019). Temperature dependence of spherical electron transfer in a nanosized [Fe₁₄] complex. Nature communications, 10(1), [5510]. https://doi.org/10.1038/s41467-019-13279-y

Huang, W, Wu, S, Gu, X, Li, Y, Okazawa, A, Kojima, N, Hayami, S, Baker, ML, Bencok, P, Noguchi, M, Miyazaki, Y, Nakano, M, Nakanishi, T , Kanegawa, S, Inagaki, Y, Kawae, T, Zhuang, GL, Shiota, Y , Yoshizawa, K, Wu, D & Sato, O 2019, 'Temperature dependence of spherical electron transfer in a nanosized [Fe₁₄] complex', Nature communications, vol. 10, no. 1, 5510. https://doi.org/10.1038/s41467-019-13279-y

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title = "Temperature dependence of spherical electron transfer in a nanosized [Fe14] complex",

abstract = "The study of transition metal clusters exhibiting fast electron hopping or delocalization remains challenging, because intermetallic communications mediated through bridging ligands are normally weak. Herein, we report the synthesis of a nanosized complex, [Fe(Tp)(CN)3]8[Fe(H2O)(DMSO)]6 (abbreviated as [Fe14], Tp−, hydrotris(pyrazolyl)borate; DMSO, dimethyl sulfoxide), which has a fluctuating valence due to two mobile d-electrons in its atomic layer shell. The rate of electron transfer of [Fe14] complex demonstrates the Arrhenius-type temperature dependence in the nanosized spheric surface, wherein high-spin centers are ferromagnetically coupled, producing an S = 14 ground state. The electron-hopping rate at room temperature is faster than the time scale of M{\"o}ssbauer measurements (<~10−8 s). Partial reduction of N-terminal high spin FeIII sites and electron mediation ability of CN ligands lead to the observation of both an extensive electron transfer and magnetic coupling properties in a precisely atomic layered shell structure of a nanosized [Fe14] complex.",

author = "Wei Huang and Shuqi Wu and Xiangwei Gu and Yao Li and Atsushi Okazawa and Norimichi Kojima and Shinya Hayami and Baker, {Michael L.} and Peter Bencok and Mariko Noguchi and Yuji Miyazaki and Motohiro Nakano and Takumi Nakanishi and Shinji Kanegawa and Yuji Inagaki and Tatsuya Kawae and Zhuang, {Gui Lin} and Yoshihito Shiota and Kazunari Yoshizawa and Dayu Wu and Osamu Sato",

note = "Funding Information: We are thankful for the financial support by the PAPD of Jiangsu Higher Education Institutions. This work is supported by the NSFC programs (Grants 21671027, 21471023 and 21671172), by MEXT KAKENHI (Grant Number JP17H01197, JP17H03117, JP16K05725 and JP18K05057), JST-CREST “Innovative Catalysts” JPMJCR15P5) and sponsored by the Jiangsu Provincial QingLan Projects. D.W. thanks Prof. Z.W. Ouyang and Dr. Z.X. Wang for assisting the HF-EPR measurements with the support by Wuhan National High Magnetic Field Center. XAS and XMCD experiments were carried out with the support of the Diamond Light Source (proposal SI17723). A portion of this work was performed on the Steady High Magnetic Field Facilities, High Magnetic Field Laboratory, CAS. Publisher Copyright: {\textcopyright} 2019, The Author(s).",

year = "2019",

month = dec,

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doi = "10.1038/s41467-019-13279-y",

language = "English",

volume = "10",

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issn = "2041-1723",

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TY - JOUR

T1 - Temperature dependence of spherical electron transfer in a nanosized [Fe14] complex

AU - Huang, Wei

AU - Wu, Shuqi

AU - Gu, Xiangwei

AU - Li, Yao

AU - Okazawa, Atsushi

AU - Kojima, Norimichi

AU - Hayami, Shinya

AU - Baker, Michael L.

AU - Bencok, Peter

AU - Noguchi, Mariko

AU - Miyazaki, Yuji

AU - Nakano, Motohiro

AU - Nakanishi, Takumi

AU - Kanegawa, Shinji

AU - Inagaki, Yuji

AU - Kawae, Tatsuya

AU - Zhuang, Gui Lin

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Wu, Dayu

AU - Sato, Osamu

N1 - Funding Information: We are thankful for the financial support by the PAPD of Jiangsu Higher Education Institutions. This work is supported by the NSFC programs (Grants 21671027, 21471023 and 21671172), by MEXT KAKENHI (Grant Number JP17H01197, JP17H03117, JP16K05725 and JP18K05057), JST-CREST “Innovative Catalysts” JPMJCR15P5) and sponsored by the Jiangsu Provincial QingLan Projects. D.W. thanks Prof. Z.W. Ouyang and Dr. Z.X. Wang for assisting the HF-EPR measurements with the support by Wuhan National High Magnetic Field Center. XAS and XMCD experiments were carried out with the support of the Diamond Light Source (proposal SI17723). A portion of this work was performed on the Steady High Magnetic Field Facilities, High Magnetic Field Laboratory, CAS. Publisher Copyright: © 2019, The Author(s).

PY - 2019/12/1

Y1 - 2019/12/1

N2 - The study of transition metal clusters exhibiting fast electron hopping or delocalization remains challenging, because intermetallic communications mediated through bridging ligands are normally weak. Herein, we report the synthesis of a nanosized complex, [Fe(Tp)(CN)3]8[Fe(H2O)(DMSO)]6 (abbreviated as [Fe14], Tp−, hydrotris(pyrazolyl)borate; DMSO, dimethyl sulfoxide), which has a fluctuating valence due to two mobile d-electrons in its atomic layer shell. The rate of electron transfer of [Fe14] complex demonstrates the Arrhenius-type temperature dependence in the nanosized spheric surface, wherein high-spin centers are ferromagnetically coupled, producing an S = 14 ground state. The electron-hopping rate at room temperature is faster than the time scale of Mössbauer measurements (<~10−8 s). Partial reduction of N-terminal high spin FeIII sites and electron mediation ability of CN ligands lead to the observation of both an extensive electron transfer and magnetic coupling properties in a precisely atomic layered shell structure of a nanosized [Fe14] complex.

AB - The study of transition metal clusters exhibiting fast electron hopping or delocalization remains challenging, because intermetallic communications mediated through bridging ligands are normally weak. Herein, we report the synthesis of a nanosized complex, [Fe(Tp)(CN)3]8[Fe(H2O)(DMSO)]6 (abbreviated as [Fe14], Tp−, hydrotris(pyrazolyl)borate; DMSO, dimethyl sulfoxide), which has a fluctuating valence due to two mobile d-electrons in its atomic layer shell. The rate of electron transfer of [Fe14] complex demonstrates the Arrhenius-type temperature dependence in the nanosized spheric surface, wherein high-spin centers are ferromagnetically coupled, producing an S = 14 ground state. The electron-hopping rate at room temperature is faster than the time scale of Mössbauer measurements (<~10−8 s). Partial reduction of N-terminal high spin FeIII sites and electron mediation ability of CN ligands lead to the observation of both an extensive electron transfer and magnetic coupling properties in a precisely atomic layered shell structure of a nanosized [Fe14] complex.

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U2 - 10.1038/s41467-019-13279-y

DO - 10.1038/s41467-019-13279-y

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AN - SCOPUS:85075966396

SN - 2041-1723

VL - 10

JO - Nature Communications

JF - Nature Communications

IS - 1

M1 - 5510

ER -

Temperature dependence of spherical electron transfer in a nanosized [Fe₁₄] complex

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