Late Lanthanide Macrocyclic Tetra-NHC Complexes

An isostructural set of macrocyclic tetra-N-heterocyclic carbene (NHC) complexes were synthesized on late lanthanides including Lu, Yb, Ho, Dy, and Gd. They were characterized by single-crystal X-ray diffraction, multinuclear NMR, electrochemistry, and SQUID magnetometry. Solid-state structures show that all complexes are in a highly distorted square-pyramidal geometry with an axial HMDS ligand. ¹H NMR for Lu, Yb, and Dy demonstrates that these geometries are maintained in solution. Electrochemical measurements on the Yb complex show that the NHCs are very strong σ-donors compared to other organometallic Yb complexes. Magnetic measurements of the Yb and Dy complexes reveal slow relaxation of the magnetization in both complexes. The highly anisotropic Dy complex possesses an energy barrier to spin reversal of 52.42 K/36.43 cm^-1 and waist-restricted hysteresis up to 2.8 K. Finally, an 18-atom macrocycle variant of the Lu complex was synthesized for comparison in reactivity and stability. These complexes are the first lanthanides prepared with macrocyclic NHCs and suggest that NHCs may be a promising ligand for developing single-molecule magnets.