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Published October 6, 2021 | Version Supplemental Material + Submitted
Journal Article Open

Pyrrolinium-Substituted Persistent Zwitterionic Ferrocenate Derivative Enabling the Application of Ferrocene Anolyte

Creators

  • 1. ROR icon Pohang University of Science and Technology
  • 2. ROR icon Seoul National University
  • 3. ROR icon California Institute of Technology

Abstract

Here, we report the imidazolium-/pyrrolinium-substituted persistent zwitterionic ferrocenate derivatives, which were characterized by electron paramagnetic resonance (EPR) and 57Fe Mössbauer spectroscopy. Additional theoretical studies on these zwitterionic ferrocenate derivatives clearly explain the origin of their thermal stability and the orbital interactions between iron and imidazolium-/pyrrolinium-substituted zwitterionic cyclopentadienyl ligand. Exploiting the facile Fe(II/I) redox chemistry, we successfully demonstrated that the pyrrolinium-substituted ferrocene derivative can be applied as an example of derivatized ferrocene anolyte for redox-flow batteries. These zwitterionic ferrocenate derivatives will not only deepen our understanding of the intrinsic chemistry of ferrocenate but have the potential to open the way for the rational design of metallocenate derivatives for various applications.

Additional Information

© 2021 American Chemical Society. Received: June 21, 2021; Accepted: September 15, 2021; Published: September 24, 2021. The X-ray crystallography analysis with synchrotron radiation was performed at the Pohang Accelerator Laboratory (PLS-II BL2D SMC beamline). This work was supported by (1) the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (No. NRF-2016H1A2A1907122 – Global Ph.D. Fellowship Program, NRF-2019R1A2C2010732, and NRF-2019M1A2A2067940), (2) Creative Materials Discovery Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (NRF-2017M3D1A1039553), (3) Institute for Basic Science (IBS-R006-A2), (4) Korea Electric Power Corporation (R20XO02-31), and (5) the postdoctoral research fellowship of POSTECH Initiative for fostering Unicorn of Research & Innovation (PIURI) project. We thank Prof. Jonas C. Peters for use of the Mössbauer spectroscopy and Dr. Ewa Pietrasiak for helpful discussions. The authors declare no competing financial interest.

Attached Files

Submitted - pyrrolinium-substituted-persistent-zwitterionic-ferrocenate-derivative-enabling-the-application-of-ferrocene-anolyte_v3.pdf

Supplemental Material - am1c11571_si_001.pdf

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am1c11571_si_001.pdf

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Additional details

Additional titles

Alternative title
The First Isolable Low-valent Ferrocene Enabling the Application of Unprecedented Ferrocene Anolyte
Alternative title
Low-Valent Ferrocenes

Identifiers

Eprint ID
109795
Resolver ID
CaltechAUTHORS:20210713-214314626

Related works

Describes
10.26434/chemrxiv.12687416.v3 (DOI)
10.26434/chemrxiv.12687416.v2 (DOI)
10.26434/chemrxiv.12687416.v1 (DOI)

Funding

National Research Foundation of Korea
NRF-2016H1A2A1907122
National Research Foundation of Korea
NRF-2019R1A2C2010732
National Research Foundation of Korea
NRF-2019M1A2A2067940
National Research Foundation of Korea
NRF-2017M3D1A1039553
Institute for Basic Science (Korea)
IBS-R006-A2
Korea Electric Power Corporation
R20XO02-31
Pohang University of Science and Technology (POSTECH)

Dates

Created
2021-07-13
Created from EPrint's datestamp field
Updated
2021-10-14
Created from EPrint's last_modified field