Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization† †Electronic supplementary information (ESI) available: Synthesis and characterization, shape calculations. Ab initio composition and g-tensors. Magnetic, spectroscopic and thermodynamic characterization. Crystal field splitting and composition. CCDC 1829110. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc03170c

• Published in: Chemical science (Cambridge) Vol. 10; no. 7; pp. 2101 - 2110
• Main Authors: Perfetti, Mauro, Gysler, Maren, Rechkemmer-Patalen, Yvonne, Zhang, Peng, Taştan, Hatice, Fischer, Florian, Netz, Julia, Frey, Wolfgang, Zimmermann, Lucas W., Schleid, Thomas, Hakl, Michael, Orlita, Milan, Ungur, Liviu, Chibotaru, Liviu, Brock-Nannestad, Theis, Piligkos, Stergios, van Slageren, Joris
• Format: Journal Article
• Language: English
• Published: Royal Society of Chemistry 12.12.2018
• Subjects: Chemistry
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c8sc03170c

We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy 2 (bpm)(fod) 6 ] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2-bipyrimidine). We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy 2 (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.