From Magnetic Chains to Sheets: The Impact of Hydrofluoric Acid Quantities in Mild Hydrothermal Synthesis on Mixed-Metal Fluoride Formation

Navindra Keerthisinghe; Gregory Morrison; Logan S. Breton; Mark D. Smith; Qiang Zhang; Melanie J. Kirkham; Vladislav V. Klepov; Hans Conrad zur Loye

doi:10.1021/acs.chemmater.4c03524

From Magnetic Chains to Sheets: The Impact of Hydrofluoric Acid Quantities in Mild Hydrothermal Synthesis on Mixed-Metal Fluoride Formation

Navindra Keerthisinghe, Gregory Morrison, Logan S. Breton, Mark D. Smith, Qiang Zhang, Melanie J. Kirkham, Vladislav V. Klepov, Hans Conrad zur Loye

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Abstract

Mixed-metal fluorides are excellent candidates for geometrically frustrated magnetic materials due to their extensive structural diversity and ability to host a plethora of low oxidation state transition metals with large magnetic moments. The utilization of the mild hydrothermal synthesis route to grow a series of mixed-metal fluorides with the general formula M^IIM₂^IIIF₈(H₂O)₂ (M^II = Co, Mn, Ni, Cu, and Zn; M^III = Cr and V), as well as a rare earth containing fluoride, CoCe₂F₁₀(H₂O)₂, is discussed. All synthesized M^IIM₂^IIIF₈(H₂O)₂ fluorides were isostructural (orthorhombic, Fmmm) with the exception of CuV₂F₈(H₂O)₂, which crystallizes in the monoclinic (C2/c) crystal system due to Jahn-Teller distortions. CoCe₂F₁₀(H₂O)₂ crystallizes in orthorhombic space group Cmce. The extreme sensitivity of the hydrothermal reaction conditions on phase formation is discussed, in particular how the volume of HF used impacts the formation of specific compositions and structure types. In addition, the complex magnetic behavior of the M^IIM₂^IIIF₈(H₂O)₂ family is discussed.

Original language	English
Pages (from-to)	2014-2025
Number of pages	12
Journal	Chemistry of Materials
Volume	37
Issue number	5
DOIs	https://doi.org/10.1021/acs.chemmater.4c03524
State	Published - Mar 11 2025

Funding

The National Science Foundation provided financial support for this work under DMR-2221403, which is gratefully acknowledged. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The beam time was allocated to Powgen BL-11A on proposal numbers IPTS-30183 and IPTS-31136. The authors are grateful to Dr. John Evans from Durham University, U.K., for his assistance with the TOPAS Rietveld refinements of ZnCr2F8(H2O)2(6). The figures were created with BioRender.com. The National Science Foundation provided financial support for this work under DMR-2221403, which is gratefully acknowledged. This research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The beam time was allocated to Powgen BL-11A on proposal numbers IPTS-30183 and IPTS-31136. The authors are grateful to Dr. John Evans from Durham University, U.K., for his assistance with the TOPAS Rietveld refinements of ZnCrF(HO)( 6 ). The figures were created with BioRender.com. 2 8 2 2

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title = "From Magnetic Chains to Sheets: The Impact of Hydrofluoric Acid Quantities in Mild Hydrothermal Synthesis on Mixed-Metal Fluoride Formation",

abstract = "Mixed-metal fluorides are excellent candidates for geometrically frustrated magnetic materials due to their extensive structural diversity and ability to host a plethora of low oxidation state transition metals with large magnetic moments. The utilization of the mild hydrothermal synthesis route to grow a series of mixed-metal fluorides with the general formula MIIM2IIIF8(H2O)2 (MII = Co, Mn, Ni, Cu, and Zn; MIII = Cr and V), as well as a rare earth containing fluoride, CoCe2F10(H2O)2, is discussed. All synthesized MIIM2IIIF8(H2O)2 fluorides were isostructural (orthorhombic, Fmmm) with the exception of CuV2F8(H2O)2, which crystallizes in the monoclinic (C2/c) crystal system due to Jahn-Teller distortions. CoCe2F10(H2O)2 crystallizes in orthorhombic space group Cmce. The extreme sensitivity of the hydrothermal reaction conditions on phase formation is discussed, in particular how the volume of HF used impacts the formation of specific compositions and structure types. In addition, the complex magnetic behavior of the MIIM2IIIF8(H2O)2 family is discussed.",

author = "Navindra Keerthisinghe and Gregory Morrison and Breton, \{Logan S.\} and Smith, \{Mark D.\} and Qiang Zhang and Kirkham, \{Melanie J.\} and Klepov, \{Vladislav V.\} and \{zur Loye\}, \{Hans Conrad\}",

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AU - Morrison, Gregory

AU - Breton, Logan S.

AU - Smith, Mark D.

AU - Zhang, Qiang

AU - Kirkham, Melanie J.

AU - Klepov, Vladislav V.

AU - zur Loye, Hans Conrad

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N2 - Mixed-metal fluorides are excellent candidates for geometrically frustrated magnetic materials due to their extensive structural diversity and ability to host a plethora of low oxidation state transition metals with large magnetic moments. The utilization of the mild hydrothermal synthesis route to grow a series of mixed-metal fluorides with the general formula MIIM2IIIF8(H2O)2 (MII = Co, Mn, Ni, Cu, and Zn; MIII = Cr and V), as well as a rare earth containing fluoride, CoCe2F10(H2O)2, is discussed. All synthesized MIIM2IIIF8(H2O)2 fluorides were isostructural (orthorhombic, Fmmm) with the exception of CuV2F8(H2O)2, which crystallizes in the monoclinic (C2/c) crystal system due to Jahn-Teller distortions. CoCe2F10(H2O)2 crystallizes in orthorhombic space group Cmce. The extreme sensitivity of the hydrothermal reaction conditions on phase formation is discussed, in particular how the volume of HF used impacts the formation of specific compositions and structure types. In addition, the complex magnetic behavior of the MIIM2IIIF8(H2O)2 family is discussed.

AB - Mixed-metal fluorides are excellent candidates for geometrically frustrated magnetic materials due to their extensive structural diversity and ability to host a plethora of low oxidation state transition metals with large magnetic moments. The utilization of the mild hydrothermal synthesis route to grow a series of mixed-metal fluorides with the general formula MIIM2IIIF8(H2O)2 (MII = Co, Mn, Ni, Cu, and Zn; MIII = Cr and V), as well as a rare earth containing fluoride, CoCe2F10(H2O)2, is discussed. All synthesized MIIM2IIIF8(H2O)2 fluorides were isostructural (orthorhombic, Fmmm) with the exception of CuV2F8(H2O)2, which crystallizes in the monoclinic (C2/c) crystal system due to Jahn-Teller distortions. CoCe2F10(H2O)2 crystallizes in orthorhombic space group Cmce. The extreme sensitivity of the hydrothermal reaction conditions on phase formation is discussed, in particular how the volume of HF used impacts the formation of specific compositions and structure types. In addition, the complex magnetic behavior of the MIIM2IIIF8(H2O)2 family is discussed.

UR - https://www.scopus.com/pages/publications/85217924098

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DO - 10.1021/acs.chemmater.4c03524

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AN - SCOPUS:85217924098

SN - 0897-4756

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JO - Chemistry of Materials

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From Magnetic Chains to Sheets: The Impact of Hydrofluoric Acid Quantities in Mild Hydrothermal Synthesis on Mixed-Metal Fluoride Formation

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