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The field of molecular magnetism has witnessed remarkable progress in the last decades, fuelled by the discovery of single-molecule magnets (SMMs).[1,2,3] Research into SMMs in the decades that followed saw the introduction of lanthanide ions into these complexes thanks to their high spin and strong intrinsic magnetic anisotropy.[4,5] Some lanthanide ions also have very specific optical properties. As f-f transitions are forbidden by Laporte's rule, their absorption and emission bands are thin, and their lifetimes are long. Among the diverse elements employed as ligands in SMMs, sulphur stands out as a particularly intriguing coordinating atom due to its soft-donor character and its potential to impact both the magnetic and luminescent properties of metal complexes.[6] The aim of this work is to develop new SMMs complexes based on Ln3+ ions and β-thioketonate ligands, and the study of the correlation between their structures and properties.[7] A new family of Ln3+ (Tb3+, Dy3+, Er3+, Yb3+) mononuclear complexes based on β-thioketonate ligands has been isolated as single crystals. Magnetic and photophysical properties of a complex have been studied and rationalized by ab initio calculations to illustrate the correlation between the metal-ion environment and their SMM behaviours (Figure 1).
[1] A. Caneschi, D. Gatteschi, R. Sessoli, A. L. Barra, L. C. Brunel, M. Guillot, J. Am. Chem. Soc. 1991, 113 (15), 5873–5874.
[2] R. Sessoli, D. Gatteschi, A. Caneschi, M. A. Novak, Nature 1993, 365 (6442), 141–143.
[3] R. Sessoli, H. L. Tsai, A. R. Schake, S. Wang, J. B. Vincent, K. Folting, D. Gatteschi, G. Christou, D. N. Hendrickson, J. Am. Chem. Soc. 1993, 115 (5), 1804–1816.
[4] N. Ishikawa, M. Sugita, T. Ishikawa, S. Koshihara, Y. Kaizu, J. Am. Chem. Soc. 2003, 125 (29), 8694–8695.
[5] R. J. Blagg, L. Ungur, F. Tuna, J. Speak, P. Comar, D. Collison, W. Wernsdorfer, E. J. L. McInnes, L. F. Chibotaru, R. E. P. Winpenny, Nat. Chem. 2013, 5 (8), 673–678.
[6] K. R. Vignesh, D. I. Alexandropoulos, B. S. Dolinar, K. R. Dunbar, Dalton Trans. 2019, 48 (9), 2872–2876.
[7] D. Guettas, F. Gendron, G. Fernandez Garcia, F. Riobé, T. Roisnel, O. Maury, G. Pilet, O. Cador, B. Le Guennic, Chem. Eur. J. 2020, 26 (19), 4389–4395.
