Magnetically Induced Binary Ferrocene with Oxidized Iron

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

doi:10.1021/jacs.3c05754

Title: Magnetically Induced Binary Ferrocene with Oxidized Iron

Journal Article · Wed Aug 02 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c05754· OSTI ID:1997961

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^[1]; Liu, Yanyao ^[2]; Tan, Kui ^[3]; Drake, Hannah ^[4]; Zhang, Guoyu ^[2]; Huang, Junjie ^[5];

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Wake Forest University, Winston-Salem, NC (United States)
Rutgers University, Piscataway, NJ (United States)
University of North Texas, Denton, TX (United States)
Texas A&M University, College Station, TX (United States)
Texas A & M University, College Station, TX (United States)
Charles University, Prague (Czech Republic)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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. Here, 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.

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Research Organization:: Wake Forest University, Winston-Salem, NC (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0019902; AC05-00OR22725; AC02-06CH11357

OSTI ID:: 1997961

Alternate ID(s):: OSTI ID: 1996656

Journal Information:: Journal of the American Chemical Society, Vol. 145, Issue 32; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
Extended X-ray absorption fine structure
Iron
Metal organic frameworks
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Sandwich compounds

Title: Magnetically Induced Binary Ferrocene with Oxidized Iron

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