Magnetically Induced Binary Ferrocene with Oxidized Iron

Saif Ullah; Stephanie Jensen; Yanyao Liu; Kui Tan; Hannah Drake; Guoyu Zhang; Junjie Huang; Jiří Klimeš; Darren M. Driscoll; Raphaël P. Hermann; Hong Cai Zhou; Jing Li; Timo Thonhauser

doi:10.1021/jacs.3c05754

Magnetically Induced Binary Ferrocene with Oxidized Iron

Saif Ullah, Stephanie Jensen, Yanyao Liu, Kui Tan, Hannah Drake, Guoyu Zhang, Junjie Huang, Jiří Klimeš, Darren M. Driscoll, Raphaël P. Hermann, Hong Cai Zhou, Jing Li, Timo Thonhauser

Neutron & X-Ray Scattering, & Thermophys

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

Ferrocene is perhaps the most popular and well-studied organometallic molecule, but our understanding of its structure and electronic properties has not changed for more than 70 years. In particular, all previous attempts of chemically oxidizing pure ferrocene by binding directly to the iron center have been unsuccessful, and no significant change in structure or magnetism has been reported. Using a metal organic framework host material, we were able to fundamentally change the electronic and magnetic structure of ferrocene to take on a never-before observed physically stretched/bent high-spin Fe(II) state, which readily accepts O₂ from air, chemically oxidizing the iron from Fe(II) to Fe(III). We also show that the binding of oxygen is reversible through temperature swing experiments. Our analysis is based on combining Mößbauer spectroscopy, extended X-ray absorption fine structure, in situ infrared, SQUID, thermal gravimetric analysis, and energy dispersive X-ray fluorescence spectroscopy measurements with ab initio modeling.

Original language	English
Pages (from-to)	18029-18035
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	145
Issue number	32
DOIs	https://doi.org/10.1021/jacs.3c05754
State	Published - Aug 16 2023

Bibliographical note

Publisher Copyright:
© 2023 American Chemical Society.

Funding

This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Materials Science and Engineering Division under award DE-SC0019902; award DE-ACO5-000R22725 is acknowledged for Mößbauer spectroscopy; EXAFS experiments were supported by the Chemical Sciences, Geosciences, and Biosciences Division and used resources of the Advanced Photon Source, a DOE user facility operated by Argonne National Laboratory under contract no. DE-AC02-06CH11357. Prof. K. Dunbar is gratefully acknowledged for providing resources and help regarding the SQUID experiments and their interpretation. Computations were performed using the WFU High Performance Computing Facility, a centrally managed computational resource with support provided in part by the University.

Funders	Funder number
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Argonne National Laboratory	DE-AC02-06CH11357
Division of Materials Sciences and Engineering	DE-ACO5-000R22725, DE-SC0019902
Chemical Sciences, Geosciences, and Biosciences Division

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abstract = "Ferrocene is perhaps the most popular and well-studied organometallic molecule, but our understanding of its structure and electronic properties has not changed for more than 70 years. In particular, all previous attempts of chemically oxidizing pure ferrocene by binding directly to the iron center have been unsuccessful, and no significant change in structure or magnetism has been reported. Using a metal organic framework host material, we were able to fundamentally change the electronic and magnetic structure of ferrocene to take on a never-before observed physically stretched/bent high-spin Fe(II) state, which readily accepts O2 from air, chemically oxidizing the iron from Fe(II) to Fe(III). We also show that the binding of oxygen is reversible through temperature swing experiments. Our analysis is based on combining M{\"o}{\ss}bauer spectroscopy, extended X-ray absorption fine structure, in situ infrared, SQUID, thermal gravimetric analysis, and energy dispersive X-ray fluorescence spectroscopy measurements with ab initio modeling.",

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AU - Zhang, Guoyu

AU - Huang, Junjie

AU - Klimeš, Jiří

AU - Driscoll, Darren M.

AU - Hermann, Raphaël P.

AU - Zhou, Hong Cai

AU - Li, Jing

AU - Thonhauser, Timo

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Magnetically Induced Binary Ferrocene with Oxidized Iron

Abstract

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