Single-molecule magnets (SMMs) containing only one metal center may represent the lower size limit for molecule-based magnetic information storage materials. Their current drawback is that all SMMs require liquid-helium cooling to show magnetic memory effects. We now report a chemical strategy to access the dysprosium metallocene cation [(CpiPr5)Dy(Cp*)]+ (CpiPr5, penta-iso-propylcyclopentadienyl; Cp*, pentamethylcyclopentadienyl), which displays magnetic hysteresis above liquid-nitrogen temperatures. An effective energy barrier to reversal of the magnetization of Ueff = 1541 wave number is also measured. The magnetic blocking temperature of TB = 80 kelvin for this cation overcomes an essential barrier toward the development of nanomagnet devices that function at practical temperatures.

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.

The discovery of materials capable of storing magnetic information at the level of single molecules and even single atoms has fueled renewed interest in the slow magnetic relaxation properties of single-molecule magnets (SMMs). The lanthanide elements, especially dysprosium, continue to play a pivotal role in the development of potential nanoscale applications of SMMs, including, for example, in molecular spintronics and quantum computing. Aside from their fundamentally fascinating physics, the realization of functional materials based on SMMs requires significant scientific and technical challenges to be overcome. In particular, extremely low temperatures are needed to observe slow magnetic relaxation, and while many SMMs possess a measurable energy barrier to reversal of the magnetization ( U), very few such materials display the important properties of magnetic hysteresis with remanence and coercivity. Werner-type coordination chemistry has been the dominant method used in the synthesis of lanthanide SMMs, and most of our knowledge and understanding of these materials is built on the many important contributions based on this approach. In contrast, lanthanide organometallic chemistry and lanthanide magnetochemistry have effectively evolved along separate lines, hence our goal was to promote a new direction in single-molecule magnetism by uniting the nonclassical organometallic synthetic approach with the traditionally distinct field of molecular magnetism. Over the last several years, our work on SMMs has focused on obtaining a detailed understanding of why magnetic materials based on the dysprosium metallocene cation building block {CpDy} display slow magnetic relaxation. Specifically, we aspired to control the SMM properties using novel coordination chemistry in a way that hinges on key considerations, such as the strength and the symmetry of the crystal field. In establishing that the two cyclopentadienyl ligands combine to provide a strongly axial crystal field, we were able to propose a robust magneto-structural correlation for understanding the properties of dysprosium metallocene SMMs. In doing so, a blueprint was established that allows U and the magnetic blocking temperature ( T) to be improved in a well-defined way. Although experimental discoveries with SMMs occur more rapidly than quantitative theory can (currently) process and explain, a clear message emanating from the literature is that a combination of the two approaches is most effective. In this Account, we summarize the main findings from our own work on dysprosium metallocene SMMs, and consider them in the light of related experimental studies and theoretical interpretations of related materials reported by other protagonists. In doing so, we aim to contribute to the nascent and healthy debate on the nature of spin dynamics in SMMs and allied molecular nanomagnets, which will be crucial for the further advancement of this vibrant research field.

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.