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Abstraction of a chloride ligand from the dysprosium metallocene [(Cpttt)2DyCl] ( 1Dy Cpttt=1,2,4-tri( tert-butyl)cyclopentadienide) by the triethylsilylium cation produces the first base-free rare-earth metallocenium cation [(Cpttt)2Dy]+ ( 2Dy) as a salt of the non-coordinating [B(C6F5)4]− anion. Magnetic measurements reveal that [ 2Dy][B(C6F5)4] is an SMM with a record anisotropy barrier up to 1277 cm−1 (1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of 2Dy is further highlighted by computational studies, which reveal this system to be the first lanthanide SMM in which all low-lying Kramers doublets correspond to a well-defined MJ value, with no significant mixing even in the higher doublets. [ABSTRACT FROM AUTHOR]

The pentagonal bipyramidal single-ion magnets (SIMs) are among the most attractive prototypes of high-performance single-molecule magnets (SMMs). Here, a fluorescence-active phosphine oxide ligand CyPh2PO (=cyclohexyl(diphenyl)phosphine oxide) was introduced into [Dy(CyPh2PO)2(H2O)5]Br3⋅2 (CyPh2PO)⋅EtOH⋅3 H2O, and combined dynamic magnetic measurement, optical characterization, ab initio calculation, and magneto-optical correlation of this high-performance pseudo- D5 h DyIII SIM with large Ueff (508(2) K) and high magnetic hysteresis temperature (19 K) were performed. This work provides a deeper insight into the rational design of promising molecular magnets. [ABSTRACT FROM AUTHOR]

The perturbation to the ligand field around the lanthanide ion may significantly contribute to the magnetic dynamics of single molecule magnets. This can be demonstrated by two typical Dy4 cluster-based single molecular magnets (SMMs), [Dy4X2(μ3-OH)2(μ-OH)2(2,2-bpt)4(H2O)4]X2·2H2O·4EtOH (X = Cl and Br for 1 and 2, respectively), which were constructed by using 3,5-bis(pyridin-2-yl)-1,2,4-triazole (2,2-bptH) as the polynuclear-chelating ligand. Alternating-current (ac) magnetic susceptibility measurements show that the energy barriers in complexes 1 and 2 were immensely enhanced by comparing with our previous work due to the optimization of the ligand field around DyIII ions. Remarkably, their high thermal active barriers at 190 K (1) and 197 K (2) under a zero applied external dc magnetic field are also among the highest within the reported tetranuclear lanthanide-based SMMs. [ABSTRACT FROM AUTHOR]

The pentagonal bipyramidal single‐ion magnets (SIMs) are among the most attractive prototypes of high performance single‐molecule magnets (SMMs). A fluorescence‐active phosphine oxide ligand is introduced, and by combining dynamic magnetic measurements, optical characterization, and ab initio calculations, the magneto‐optical correlation of a high‐performance pseudo‐D5h DyIII SIM with large Ueff = 508(2) K and high magnetic hysteresis temperature of 19 K, [Dy(CyPh2PO)2(H2O)5]Br3⋅2 (CyPh2PO)⋅EtOH⋅3 H2O (CyPh2PO=cyclohexyl(diphenyl)phosphine oxide) was studied. This work provides a deeper insight into the rational design of promising molecular magnets. More information can be found in the Full Paper by M.‐L. Tong, J.‐L. Liu, et al. on page 5708 ff. [ABSTRACT FROM AUTHOR]