Calder Stuart, Baral Raju, Buchanan C Charlotte, Gilbert Dustin A, Terry Rylan J, Kolis Joseph W, Sanjeewa Liurukara D
Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA.
Materials Science and Engineering, University of Tennessee, Knoxville, TN 37996, USA.
Acta Crystallogr B Struct Sci Cryst Eng Mater. 2024 Oct 1;80(Pt 5):430-442. doi: 10.1107/S2052520624008023. Epub 2024 Sep 18.
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)·2DO, which was one of the first magnetic MOFs to be investigated with neutron diffraction, is reinvestigated as an exemplar case.
材料所采用的磁结构取决于对称性、磁性离子之间交换相互作用的层级以及局域各向异性。控制磁相互作用的直接途径是在材料中实现维度控制,从零维孤立的磁性离子、一维(1D)自旋链、二维(2D)层到三维(3D)有序结构。能够针对感兴趣的现象设计具有特定维度的材料并非易事。虽然无机磁性材料领域已取得诸多进展,但有机化合物为材料设计提供了独特且可能更具潜力的基础。特别是磁性金属有机框架(mMOF)在结构框架内的有机连接体上将磁性与非磁性功能相结合,可通过压力和磁场的轻微扰动进一步调节以诱导相变。在此,研究了在更广泛的三维晶体框架内磁性离子处于二维层状环境时,如何利用对mMOF的中子散射测量来直接确定磁结构。作为示例,重新研究了氘代水合甲酸盐Co(DCOO)·2D₂O,它是最早用中子衍射研究的磁性MOF之一。