We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy2(bpm)(fod)6] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2'-bipyrimidine). Ab initio calculations were used to obtain a global picture of the electronic structure and to predict possible single molecule magnet behaviour, confirmed by experiments. The orientation of the susceptibility tensor was determined by means of cantilever torque magnetometry. An experimental determination of the electronic structure of the lanthanide ion was obtained combining Luminescence, Far Infrared and Magnetic Circular Dichroism spectroscopies. Fitting these energies to the full single ion plus crystal field Hamiltonian allowed determination of the eigenstates and crystal field parameters of a lanthanide complex without symmetry idealization. We then discuss the impact of a stepwise symmetry idealization on the modelling of the experimental data. This result is particularly important in view of the misleading outcomes that are often obtained when the symmetry of lanthanide complexes is idealized.

Department of Chemistry University of Copenhagen Universitetsparken 5 2100 Denmark

Institut für Anorganische Chemie Universität Stuttgart Pfaffenwaldring 55 D 70569 Stuttgart Germany

Institut für Organische Chemie Universität Stuttgart Pfaffenwaldring 55 D 70569 Stuttgart Germany

Institut für Physikalische Chemie Universität Stuttgart Pfaffenwaldring 55 D 70569 Stuttgart Germany Email

Institute of Physics Charles University Ke Karlovu 5 12116 Praja 2 Czech Republic

Laboratoire National des Champs Magnétiques Intenses CNRS UGA 38042 Grenoble France

Theory of Nanomaterials Group Katholieke Universiteit Leuven Celestijnenlaan 220F 3001 Leuven Belgium

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Chem Sci. 2019 Mar 1;10(11):3429. doi: 10.1039/c9sc90051a. PubMed

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