Dipolar Coupling as a Mechanism for Fine Control of Magnetic States in ErCOT-Alkyl Molecular Magnets

The design of molecular magnets has progressed greatly by taking advantage of the ability to impart successive perturbations and control vibronic transitions in 4f systems through the careful manipulation of the crystal field. Herein, we control the orientation and rigidity of two dinuclear ErCOT-based molecular magnets: the inversion-symmetric bridged [ErCOT(μ-Me)(THF)]₂ (2) and the nearly linear Li[(ErCOT)₂(μ-Me)₃] (3). The conserved anisotropy of the ErCOT synthetic unit facilitates the direction of the arrangement of its magnetic anisotropy for the purposes of generating controlled internal magnetic fields, improving control of the energetics and transition probabilities of the electronic angular momentum states with exchange biasing via dipolar coupling. This control is evidenced through the introduction of a second thermal barrier to relaxation operant at low temperatures that is twice as large in 3 as in 2. This barrier acts to suppress through-barrier relaxation by protecting the ground state from interacting with stray local fields while operating at an energy scale an order of magnitude smaller than the crystal field term. These properties are highlighted when contrasted against the mononuclear structure ErCOT(Bn)(THF)₂ (1), in which quantum tunneling of the magnetization processes dominate, as demonstrated by magnetometry and ab initio computational methods. Furthermore, far-infrared magnetospectroscopy measurements reveal that the increased rigidity imparted by successive removal of solvent ligands when adding bridging methyl groups, along with the increased excited state purity, severely limits local spin-vibrational interactions that facilitate magnetic relaxation, manifesting as longer relaxation times in 3 relative to those in 2 as temperature is increased.