Importance of Axial Symmetry in Elucidating Lanthanide-Transition Metal Interactions

Bonde, N. A.; Petersen, J. B.; Sorensen, M. A.; Nielsen, U. G.; Fak, B.; Rols, S.; Ollivier, J.; Weihe, Ho.; Bendix, J.; Perfetti, M.

doi:10.1021/acs.inorgchem.9b02064

In this paper, we experimentally study and model the electron donating character of an axial diamagnetic Pd2+ ion in four metalloligated lanthanide complexes of formula [PPh4][Ln{Pd(SAc)4}2] (SAc- = thioacetate, Ln = Tb, Dy, Ho, and Er). A global model encompassing inelastic neutron scattering, torque magnetometry, and dc magnetometry allows to precisely determine the energy level structure of the complexes. Solid state nuclear magnetic resonance reveals a less donating character of Pd2+ compared to the previously reported isostructural Pt2+-based complexes. Consequently, all complexes invariably show a lower crystal field strength compared to their Pt2+-analogues. The dynamic properties show an enhanced single molecule magnet behavior due to the suppression of quantum tunneling, in agreement with our model.

Importance of Axial Symmetry in Elucidating Lanthanide-Transition Metal Interactions / Bonde N.A.; Petersen J.B.; Sorensen M.A.; Nielsen U.G.; Fak B.; Rols S.; Ollivier J.; Weihe Ho.; Bendix J.; Perfetti M.. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - ELETTRONICO. - 59:(2020), pp. 235-243. [10.1021/acs.inorgchem.9b02064]