Low-dimensional metal–organic frameworks: a pathway to design, explore and tune magnetic structures

Stuart Calder; Raju Baral; C. Charlotte Buchanan; Dustin A. Gilbert; Rylan J. Terry; Joseph W. Kolis; Liurukara D. Sanjeewa

doi:10.1107/S2052520624008023

Low-dimensional metal–organic frameworks: a pathway to design, explore and tune magnetic structures

Stuart Calder, Raju Baral, C. Charlotte Buchanan, Dustin A. Gilbert, Rylan J. Terry, Joseph W. Kolis, Liurukara D. Sanjeewa

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Abstract

The magnetic structure adopted by a material relies on symmetry, the hierarchy of exchange interactions between magnetic ions and local anisotropy. A direct pathway to control the magnetic interactions is to enforce dimensionality within the material, from zero-dimensional isolated magnetic ions, one-dimensional (1D) spin-chains, two-dimensional (2D) layers to three-dimensional (3D) order. Being able to design a material with a specific dimensionality for the phenomena of interest is non-trivial. While many advances have been made in the area of inorganic magnetic materials, organic compounds offer distinct and potentially more fertile ground for material design. In particular magnetic metal–organic frameworks (mMOFs) combine magnetism with non-magnetic property functionality on the organic linkers within the structural framework, which can further be tuned with mild perturbations of pressure and field to induce phase transitions. Here, it is examined how neutron scattering measurements on mMOFs can be used to directly determine the magnetic structure when the magnetic ions are in a 2D layered environment within the wider 3D crystalline framework. The hydrated formate, in deuterated form, Co(DCOO)₂·2D₂O, which was one of the first magnetic MOFs to be investigated with neutron diffraction, is reinvestigated as an exemplar case.

Original language	English
Pages (from-to)	430-442
Number of pages	13
Journal	Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials
Volume	80
DOIs	https://doi.org/10.1107/S2052520624008023
State	Published - Oct 1 2024

Funding

This research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paidup, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doepublic-access-plan). The work at University of Missouri and Clemson University was supported by awards from the NSF DMR \u2013 2219129. Magnetic measurements taken at the University of Tennessee were supported by the DOE Early Career Program, Award DE-SC0021344. This manuscript has been authored by UTBattelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy.

Funders	Funder number
United States Government
DOE Public Access Plan
Oak Ridge National Laboratory
Office of Science
National Science Foundation	DMR – 2219129
National Science Foundation
U.S. Department of Energy	DE-AC05-00OR22725, DE-SC0021344
U.S. Department of Energy

Keywords

magnetism
metal–organic frameworks
neutron diffraction
polarization

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10.1107/S2052520624008023

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abstract = "The magnetic structure adopted by a material relies on symmetry, the hierarchy of exchange interactions between magnetic ions and local anisotropy. A direct pathway to control the magnetic interactions is to enforce dimensionality within the material, from zero-dimensional isolated magnetic ions, one-dimensional (1D) spin-chains, two-dimensional (2D) layers to three-dimensional (3D) order. Being able to design a material with a specific dimensionality for the phenomena of interest is non-trivial. While many advances have been made in the area of inorganic magnetic materials, organic compounds offer distinct and potentially more fertile ground for material design. In particular magnetic metal–organic frameworks (mMOFs) combine magnetism with non-magnetic property functionality on the organic linkers within the structural framework, which can further be tuned with mild perturbations of pressure and field to induce phase transitions. Here, it is examined how neutron scattering measurements on mMOFs can be used to directly determine the magnetic structure when the magnetic ions are in a 2D layered environment within the wider 3D crystalline framework. The hydrated formate, in deuterated form, Co(DCOO)2·2D2O, which was one of the first magnetic MOFs to be investigated with neutron diffraction, is reinvestigated as an exemplar case.",

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Low-dimensional metal–organic frameworks: a pathway to design, explore and tune magnetic structures

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