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
Institut für Physikalische Chemie , Universität Stuttgart , Pfaffenwaldring 55 , D-70569 Stuttgart , Germany . Email:
Institut für Organische Chemie , Universität Stuttgart , Pfaffenwaldring 55 , D-70569 Stuttgart , Germany.
Chem Sci. 2018 Dec 12;10(7):2101-2110. doi: 10.1039/c8sc03170c. eCollection 2019 Feb 21.
We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy(bpm)(fod)] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2'-bipyrimidine). 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.
我们展示了对发光且易挥发的基于镝的单分子磁体[Dy(bpm)(fod)]（Hfod = 6,6,7,7,8,8,8 - 七氟 - 2,2 - 二甲基 - 3,5 - 辛二酮，bpm = 2,2'-联嘧啶）的磁性和电子结构的深入测定。通过计算获得电子结构的全局图像并预测可能的单分子磁体行为，这一点得到了实验的证实。通过悬臂扭矩磁强计确定了磁化率张量的方向。结合发光光谱、远红外光谱和磁圆二色光谱对镧系离子的电子结构进行了实验测定。将这些能量拟合到完整的单离子加晶体场哈密顿量中，无需进行对称性理想化即可确定镧系配合物的本征态和晶体场参数。然后我们讨论了逐步对称性理想化对实验数据建模的影响。鉴于在理想化镧系配合物对称性时经常获得的误导性结果，这一结果尤为重要。
