Pseudo-Polymorphism in Layered FeS Intercalates: A Competition between Charged and Neutral Guest Species
Abstract
Systematic synthesis studies of the formation of tetrahedral FeS-ethylenediamine intercalates resulted in the synthesis of a new compound, [Fe9.4(2)S10][Fe(en)3]0.6(1)·en0.9(3). The composition and complex crystal structure were determined based on a synergistic combination of elemental composition, decomposition behavior, high-resolution synchrotron X-ray diffraction and total scattering, 57Fe Mössbauer spectroscopy, and electron diffraction. The structural model was derived based on a systematic comparison to the previously reported structures [Fe8S10][Fe(en)3]1·en0.5 and tetragonal FeS. The new compound has flat Fe9.4S10 layers, analogous to those in superconducting binary FeS. In the crystal structure of [Fe9.4S10][Fe(en)3]0.6·en0.9, the interlayer space is occupied by [Fe(en)3]2+ complexes and neutral ethylenediamine molecules in a ~2:3 ratio. Interlayer species are not randomly oriented but ordered as evidenced by superstructural diffraction peaks in both high-resolution X-ray diffraction and electron diffraction patterns. Magnetic studies reveal no superconducting transition down to 2 K, indicating that the presence of minute amounts (~6%) of iron vacancies at the Fe-S layer in [Fe9.4S10][Fe(en)3]0.6·en0.9 is still sufficient to shift the position of the Fermi level resulting in an adjustment of the properties. Here, our work shows the importance of detailed characterization of the crystal structure of intercalated compounds to understand the origin of the observed properties and develop propermore »
- Authors:
-
[1];
[4];
[5];
[1]
- Ames Laboratory, and Iowa State University, Ames, IA (United States)
- University of Tennessee, Knoxville, TN (United States); Middle Tennessee State University, Murfreesboro, TN (United States)
- Laboratoire de Cristallographie et Sciences des Matériaux, CAEN (France)
- Ames Laboratory, and Iowa State University, Ames, IA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Iowa State University, Ames, IA (United States)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States); Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1907152
- Report Number(s):
- IS-J-10,847
Journal ID: ISSN 0897-4756
- Grant/Contract Number:
- AC02-06CH11357; AC02-07CH11358; SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 34; Journal Issue: 12; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Harmer, Colin P., Kamali, Saeed, Lebedev, Oleg I., Lee, Shannon J., Ribeiro, Raquel A., Canfield, Paul C., and Kovnir, Kirill. Pseudo-Polymorphism in Layered FeS Intercalates: A Competition between Charged and Neutral Guest Species. United States: N. p., 2022.
Web. doi:10.1021/acs.chemmater.2c00270.
Harmer, Colin P., Kamali, Saeed, Lebedev, Oleg I., Lee, Shannon J., Ribeiro, Raquel A., Canfield, Paul C., & Kovnir, Kirill. Pseudo-Polymorphism in Layered FeS Intercalates: A Competition between Charged and Neutral Guest Species. United States. https://doi.org/10.1021/acs.chemmater.2c00270
Harmer, Colin P., Kamali, Saeed, Lebedev, Oleg I., Lee, Shannon J., Ribeiro, Raquel A., Canfield, Paul C., and Kovnir, Kirill. Tue .
"Pseudo-Polymorphism in Layered FeS Intercalates: A Competition between Charged and Neutral Guest Species". United States. https://doi.org/10.1021/acs.chemmater.2c00270. https://www.osti.gov/servlets/purl/1907152.
@article{osti_1907152,
title = {Pseudo-Polymorphism in Layered FeS Intercalates: A Competition between Charged and Neutral Guest Species},
author = {Harmer, Colin P. and Kamali, Saeed and Lebedev, Oleg I. and Lee, Shannon J. and Ribeiro, Raquel A. and Canfield, Paul C. and Kovnir, Kirill},
abstractNote = {Systematic synthesis studies of the formation of tetrahedral FeS-ethylenediamine intercalates resulted in the synthesis of a new compound, [Fe9.4(2)S10][Fe(en)3]0.6(1)·en0.9(3). The composition and complex crystal structure were determined based on a synergistic combination of elemental composition, decomposition behavior, high-resolution synchrotron X-ray diffraction and total scattering, 57Fe Mössbauer spectroscopy, and electron diffraction. The structural model was derived based on a systematic comparison to the previously reported structures [Fe8S10][Fe(en)3]1·en0.5 and tetragonal FeS. The new compound has flat Fe9.4S10 layers, analogous to those in superconducting binary FeS. In the crystal structure of [Fe9.4S10][Fe(en)3]0.6·en0.9, the interlayer space is occupied by [Fe(en)3]2+ complexes and neutral ethylenediamine molecules in a ~2:3 ratio. Interlayer species are not randomly oriented but ordered as evidenced by superstructural diffraction peaks in both high-resolution X-ray diffraction and electron diffraction patterns. Magnetic studies reveal no superconducting transition down to 2 K, indicating that the presence of minute amounts (~6%) of iron vacancies at the Fe-S layer in [Fe9.4S10][Fe(en)3]0.6·en0.9 is still sufficient to shift the position of the Fermi level resulting in an adjustment of the properties. Here, our work shows the importance of detailed characterization of the crystal structure of intercalated compounds to understand the origin of the observed properties and develop proper structure–property relationships.},
doi = {10.1021/acs.chemmater.2c00270},
journal = {Chemistry of Materials},
number = 12,
volume = 34,
place = {United States},
year = {Tue Jun 07 00:00:00 EDT 2022},
month = {Tue Jun 07 00:00:00 EDT 2022}
}
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