Tuning Fe–Se Tetrahedral Frameworks by a Combination of [Fe(en)3]2+ Cations and Cl– Anions
Abstract
A one-dimensional (1D) chain compound (en = ethylenediamine), featuring tetrahedral FeSe2 chains separated by [Fe(en)3]2+ cations and Cl– anions, has been synthesized by a low temperature solvothermal method using simple starting materials. The degree of distortion in the Fe–Se backbone is similar to previously reported compounds with isolated 1D FeSe2 chains. 57Fe Mössbauer spectroscopy reveals the mixed-valent nature of [Fe(en)3]3(FeSe2)4Cl2 with Fe3+ centers in the [FeSe2]- chains and Fe2+ centers in the [Fe(en)3]2+ complexes. SQUID magnetometry indicates that is paramagnetic with a reduced average effective magnetic moment, μeff = 9.51 μB per formula unit, and a negative Weiss constant, θ = -10.9(4) K, indicating antiferromagnetic (AFM) nearest neighbor interactions within the [FeSe2]- chains. Furthermore, weak antiferromagnetic coupling between chains, combined with rather strong intrachain AFM coupling, leads to spin-glass behavior at low temperatures, as indicated by a frequency shift of the peak observed at 3 K in AC magnetic measurements. A combination of [Fe(en)3]2+ and Cl– ions is also capable of stabilizing mixed-valent 2D Fe–Se puckered layers in the crystal structure of [Fe(en)3]4(Fe14Se21)Cl2, where Fe14Se21 layers have a unique topology with large open pores. Property measurements of [Fe(en)3]4(Fe14Se21)Cl2 could not be performed due to the inability to either grow largemore »
- Authors:
-
[1];
[5];
[1]
- Ames Lab., and Iowa State Univ., Ames, IA (United States)
- Univ. of California, Davis, CA (United States)
- Univ. of Tennessee Space Inst., Tullahoma, TN (United States); Middle Tennessee State Univ., Murfreesboro, TN (United States)
- Florida State Univ., Tallahassee, FL (United States)
- Florida State Univ., Tallahassee, FL (United States); Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1668259
- Report Number(s):
- IS-J-10,299
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- AC02-07CH11358; DMR-1905499; DMR-2003783; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 59; Journal Issue: 18; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Anions; crystal structure; magnetic properties; physical and chemical processes; cations
Citation Formats
Gamage, Eranga H., Greenfield, Joshua T., Unger, Colin, Kamali, Saeed, Clark, Judith K., Harmer, Colin P., Luo, Liang, Wang, Jigang, Shatruk, Michael, and Kovnir, Kirill. Tuning Fe–Se Tetrahedral Frameworks by a Combination of [Fe(en)3]2+ Cations and Cl– Anions. United States: N. p., 2020.
Web. doi:10.1021/acs.inorgchem.0c01727.
Gamage, Eranga H., Greenfield, Joshua T., Unger, Colin, Kamali, Saeed, Clark, Judith K., Harmer, Colin P., Luo, Liang, Wang, Jigang, Shatruk, Michael, & Kovnir, Kirill. Tuning Fe–Se Tetrahedral Frameworks by a Combination of [Fe(en)3]2+ Cations and Cl– Anions. United States. https://doi.org/10.1021/acs.inorgchem.0c01727
Gamage, Eranga H., Greenfield, Joshua T., Unger, Colin, Kamali, Saeed, Clark, Judith K., Harmer, Colin P., Luo, Liang, Wang, Jigang, Shatruk, Michael, and Kovnir, Kirill. Tue .
"Tuning Fe–Se Tetrahedral Frameworks by a Combination of [Fe(en)3]2+ Cations and Cl– Anions". United States. https://doi.org/10.1021/acs.inorgchem.0c01727. https://www.osti.gov/servlets/purl/1668259.
@article{osti_1668259,
title = {Tuning Fe–Se Tetrahedral Frameworks by a Combination of [Fe(en)3]2+ Cations and Cl– Anions},
author = {Gamage, Eranga H. and Greenfield, Joshua T. and Unger, Colin and Kamali, Saeed and Clark, Judith K. and Harmer, Colin P. and Luo, Liang and Wang, Jigang and Shatruk, Michael and Kovnir, Kirill},
abstractNote = {A one-dimensional (1D) chain compound (en = ethylenediamine), featuring tetrahedral FeSe2 chains separated by [Fe(en)3]2+ cations and Cl– anions, has been synthesized by a low temperature solvothermal method using simple starting materials. The degree of distortion in the Fe–Se backbone is similar to previously reported compounds with isolated 1D FeSe2 chains. 57Fe Mössbauer spectroscopy reveals the mixed-valent nature of [Fe(en)3]3(FeSe2)4Cl2 with Fe3+ centers in the [FeSe2]- chains and Fe2+ centers in the [Fe(en)3]2+ complexes. SQUID magnetometry indicates that is paramagnetic with a reduced average effective magnetic moment, μeff = 9.51 μB per formula unit, and a negative Weiss constant, θ = -10.9(4) K, indicating antiferromagnetic (AFM) nearest neighbor interactions within the [FeSe2]- chains. Furthermore, weak antiferromagnetic coupling between chains, combined with rather strong intrachain AFM coupling, leads to spin-glass behavior at low temperatures, as indicated by a frequency shift of the peak observed at 3 K in AC magnetic measurements. A combination of [Fe(en)3]2+ and Cl– ions is also capable of stabilizing mixed-valent 2D Fe–Se puckered layers in the crystal structure of [Fe(en)3]4(Fe14Se21)Cl2, where Fe14Se21 layers have a unique topology with large open pores. Property measurements of [Fe(en)3]4(Fe14Se21)Cl2 could not be performed due to the inability to either grow large crystals or synthesize this material in single-phase form.},
doi = {10.1021/acs.inorgchem.0c01727},
journal = {Inorganic Chemistry},
number = 18,
volume = 59,
place = {United States},
year = {Tue Sep 01 00:00:00 EDT 2020},
month = {Tue Sep 01 00:00:00 EDT 2020}
}
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