Are Inorganic Single-Molecule Magnets a Possibility? A Theoretical Insight into Dysprosium Double-Deckers with Inorganic Ring Systems

Computational studies
of sandwich dysprosium double-decker complexes
[Dy­(L)2]+/3+ as candidates for single-ion magnets
with several inorganic aromatic ring systems (P5–, N5–, B3N3H6, B3P3H6, B3S3H3) have been performed. The molecular structures
were optimized with the TPSSh functional, and the ground state properties
were investigated with the complete active space SCF method (CASSCF)
complemented by the dynamic correlation dressed correction (DCD-CAS(2))
or NEVPT2. Besides the evaluation of the magnetic moment blocking
barrier, the impact of the molecular vibration on the relaxation of
magnetization was also inspected. We were able to make predictions
about the performance of those molecules as single-molecule magnets,
where estimated effective energy barrier, Ueff, values are as high as 1475 K in the case of [Dy­(N5)2]−, which is the most anisotropic complex
from our choice of studied compounds, making them a potentially very
effective carbon-free alternative to organometallic double-decker
dysprosocenium high-temperature single-molecule magnets.