David P. Mills
Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Email: david.mills@manchester.ac.uk
Website: millsgroup.weebly.com
Twitter: @millsgroupchem
The complexity and richness of synthetic f-element chemistry has attracted increasing attention in recent years. This interest is stimulated jointly by scientific curiosity of a relatively unexplored field and the myriad applications that these elements have found in diverse areas such as organic synthesis, materials science, and nuclear fuel cycles1.
Our research focuses on stabilizing lanthanide (Ln) and actinide (An) complexes with unusual coordination geometries and/or oxidation states, which can provide enhanced reactivity and unique physical properties, including interesting single-molecule magnet (SMM) behaviour in highly axial Ln complexes. We mainly use bulky bis(silyl)amides and cyclopentadienyls as supporting ligands to stabilize these unusual f-element motifs. Here we will present some recent highlights, such as rare formally two-coordinate Ln complexes2, and isolated Ln(III) metallocenium cations2, which provided record magnetic hysteresis temperatures for the dysprosium analogue 2-Dy in 2017 and new design criteria for high-performance SMMs3.
(1) Example of a rare Ln complex.
(2) Isolated Ln(III) metallocenium cation structure.
References
- The Lanthanides and Actinides, Ed. S. T. Liddle, D. P. Mills, L. S. Natrajan, World Scientific Publishing Europe Ltd, Singapore, 2022.
- See for example: (a) H. M. Nicholas, M. Vonci, C. A. P. Goodwin, et al., Chem. Sci., 2019, 10, 10493; (b) J. Emerson-King, G. K. Gransbury, et al., J. Am. Chem. Soc., 2024, 146, 3331.
- See for example: (a) C. A. P. Goodwin, F. Ortu, D. Reta, et al., Nature, 2017, 548, 439; (b) C. A. P. Goodwin, D. Reta, et al., J. Am. Chem. Soc., 2017, 139, 18714.
