Metal–ligand pair anisotropy in a series of mononuclear Er–COT complexes

Abstract

Synthetic control of the crystal field has elevated lanthanides to the forefront of single-molecule magnet (SMM) research, yet the resultant strong, predictable single-ion anisotropy has thus far not translated into equally impressive molecule-based magnets of higher dimensionality. This roadblock arises from the dual demands made of the crystal field: generate anisotropy and facilitate magnetic coupling. Here we demonstrate that particular metal–ligand pairs can dominate the single-ion electronic structure so fully that the remaining coordination sphere plays a minimal role in the magnitude and orientation of the magnetic anisotropy. This Metal–Ligand Pair Anisotropy (MLPA) effectively separates the crystal field into discrete components dedicated to anisotropy and magnetic coupling. To demonstrate an MLPA building unit, we synthesized four new mononuclear complexes that challenge the electronic structure of the iconic lanthanocene ([Ln(COT)₂]⁺; COT²⁻ = cyclooctatetraene dianion) complex which is known to generate strong anisotropy with Ln = Er³⁺. Variation in symmetry and coordination strength for Er(COT)I(THF)₂ (THF = tetrahydrofuran) (1), Er(COT)I(Py)₂ (Py = pyridine) (2), Er(COT)I(MeCN)₂ (MeCN = acetonitrile) (3), and Er(COT)(Tp*) (Tp* = tris(3,5-dimethyl-1-pyrazolyl)borate) (4) shows that the Er–COT unit stabilizes anisotropy despite deliberate de-optimization. All four half-sandwich complexes display SMM behavior with effective energy barriers of U_eff = 95.6(9), 102.9(3.1), 107.1(1.3), and 133.6(2.2) cm⁻¹ for 1–4 by a multi-relaxation-process fitting. More importantly, the basic state splittings remain intact and the anisotropy axes are within several degrees of normal to the COT²⁻ ring according to complete active space self-consistent field (CASSCF) calculations. Further investigation of the MLPA conceptual framework is warranted as it can provide building units with well-defined magnetic orientation and strength. We envision that the through-barrier processes observed herein, such as quantum tunneling, can be mitigated by formation of larger clusters and molecule-based materials.