Recent Developments in CoIII2LnIII2 Single‐Molecule Magnets

• Published in: European journal of inorganic chemistry Vol. 2018; no. 20-21; pp. 2067 - 2089
• Main Authors: Funes, Alejandro V., Alborés, Pablo
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 07.06.2018
• Subjects: Cobalt; Inorganic chemistry; Lanthanides; Magnetic properties; Magnets; Mathematical analysis; Molecular chains; Single‐molecule magnets; Slow relaxation
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201800253

In this work we review the Co2IIILn2III family of compounds reported up to date that shows SMM features. The vast majority of them show a butterfly arrangement with LnIII ions placed at the body positions. The number of DyIII examples constitutes the majority, probably because of the intrinsic properties of this lanthanide ion regarding SMMs characteristics. Butterfly complexes have a SAP geometry around LnIII ions with a variety of distortion degrees. However, when looking at the key Ueff parameter trend through this family of complexes, it becomes clear that a pure geometrical consideration is not enough to explain it. Ab initio based calculations provide evidence of highly anisotropic mJ ground states for complexes where LnIII = DyIII, pointing to exclusively mJ = 15/2 ground Kramers doublets. These calculations also agree with the thermally activated relaxation involving the first excited state and, in some examples where multiple relaxation pathways are observed, higher excited states. A few examples prove that Raman and/or direct mechanisms cannot be discarded a priori. Only two examples of isostructural LnIII families of the same Co2IIILn2III complex can be found. We review the Co2IIILn2III family of compounds reported up to date that shows SMM features, emphasizing structural variety and its relationship with magnetization slow relaxation processes, discussing experimental and theoretical information.