Putting the Squeeze on Molecule-Based Magnets: Exploiting Pressure to Develop Magneto-Structural Correlations in Paramagnetic Coordination Compounds

• Published in: Magnetochemistry 2020-09, Vol.6 (3), p.32
• Main Authors: Etcheverry-Berrios, Alvaro, Parsons, Simon, Kamenev, Konstantin V., Probert, Michael R., Moggach, Stephen A., Murrie, Mark, Brechin, Euan K.
• Format: Article
• Language: English
• Subjects: Coordination compounds; Correlation; Crystal lattices; Crystal structure; Crystallography; Depolymerization; Electron paramagnetic resonance; External pressure; high pressure absorption spectroscopy; high pressure magnetometry; high pressure X-ray crystallography; Hydrostatic pressure; Inelastic scattering; Jahn-Teller effect; Ligands; Magnetic anisotropy; Magnetic cores; Magnetic measurement; Magnetic permeability; Magnetic properties; Magnetism; Magnets; molecule-based magnets; Neutron scattering; Phase transitions; Physical properties; Raman spectroscopy; Resonance scattering; Single crystals; single-ion magnets; single-molecule magnets; Studies
• ISSN: 2312-7481; 2312-7481
• DOI: 10.3390/magnetochemistry6030032

The cornerstone of molecular magnetism is a detailed understanding of the relationship between structure and magnetic behaviour, i.e., the development of magneto-structural correlations. Traditionally, the synthetic chemist approaches this challenge by making multiple compounds that share a similar magnetic core but differ in peripheral ligation. Changes in the ligand framework induce changes in the bond angles and distances around the metal ions, which are manifested in changes to magnetic susceptibility and magnetisation data. This approach requires the synthesis of a series of different ligands and assumes that the chemical/electronic nature of the ligands and their coordination to the metal, the nature and number of counter ions and how they are positioned in the crystal lattice, and the molecular and crystallographic symmetry have no effect on the measured magnetic properties. In short, the assumption is that everything outwith the magnetic core is inconsequential, which is a huge oversimplification. The ideal scenario would be to have the same complex available in multiple structural conformations, and this is something that can be achieved through the application of external hydrostatic pressure, correlating structural changes observed through high-pressure single crystal X-ray crystallography with changes observed in high-pressure magnetometry, in tandem with high-pressure inelastic neutron scattering (INS), high-pressure electron paramagnetic resonance (EPR) spectroscopy, and high-pressure absorption/emission/Raman spectroscopy. In this review, which summarises our work in this area over the last 15 years, we show that the application of pressure to molecule-based magnets can (reversibly) (1) lead to changes in bond angles, distances, and Jahn–Teller orientations; (2) break and form bonds; (3) induce polymerisation/depolymerisation; (4) enforce multiple phase transitions; (5) instigate piezochromism; (6) change the magnitude and sign of pairwise exchange interactions and magnetic anisotropy, and (7) lead to significant increases in magnetic ordering temperatures.