Damgaard-Møller Emil, Krause Lennard, Lassen Helene, Malaspina Lorraine A, Grabowsky Simon, Bamberger Heiko, McGuire Jake, Miras Haralampos N, Sproules Stephen, Overgaard Jacob
Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Aarhus C, Denmark.
Department 2-Biology/Chemistry, University of Bremen, Leobener Str. 3, 28359 Bremen, Germany.
Inorg Chem. 2020 Sep 21;59(18):13190-13200. doi: 10.1021/acs.inorgchem.0c01489. Epub 2020 Sep 1.
Understanding magnetic anisotropy and specifically how to tailor it is crucial in the search for high-temperature single-ion magnets. Herein, we investigate the magnetic anisotropy in a six-coordinated cobalt(II) compound that has a complex geometry and distinct triaxial magnetic anisotropy from the perspective of the electronic structure, using electronic spectra, ab initio calculations, and an experimental charge density, of which the latter two provides insight into the d-orbital splitting. The analysis showed that the d-orbital splitting satisfactorily predicted the complex triaxial magnetic anisotropy exhibited by the compound. Furthermore, a novel method to directly compare the ab initio results and the d-orbital populations obtained from the experimental charge density was developed, while a topological analysis of the density provided insights into the metal-ligand bonding. This work thus further establishes the validity of using d-orbitals for predicting magnetic anisotropy in transition metal compounds while also pointing out the need for a more frequent usage of the term triaxial anisotropy in the field of single-molecule magnetism.
了解磁各向异性，特别是如何对其进行调控，对于寻找高温单离子磁体至关重要。在此，我们从电子结构的角度，利用电子光谱、从头算计算和实验电荷密度，研究了一种具有复杂几何结构和独特三轴磁各向异性的六配位钴（II）化合物中的磁各向异性，其中后两者有助于深入了解d轨道分裂。分析表明，d轨道分裂令人满意地预测了该化合物所表现出的复杂三轴磁各向异性。此外，还开发了一种直接比较从头算结果和从实验电荷密度获得的d轨道占据数的新方法，同时对密度进行拓扑分析有助于深入了解金属-配体键合。因此，这项工作进一步确立了利用d轨道预测过渡金属化合物磁各向异性的有效性，同时也指出在单分子磁体领域更频繁使用术语“三轴各向异性”的必要性。
