Nanostructuring of Dysprosocenium Single-Ion Magnets through Encapsulation in MOFs: A Promising Approach to Achieve High Axiality and Ambient Stability with Long-Range Ordering

Implementing magnetic bistability in single-molecule magnets (SMMs) for quantum technologies requires precise nanostructuring, spatial organization, and environmental stabilization of magnetic centers. Here, we report the first encapsulation of the lanthanide-based [Dy(Cp*)₂]⁺ SMM in three mesoporous diamagnetic MOFs─NU-1000, PCN-222-Zn, and MOF-177─to design hybrid magnetic structures with long-range ordering. An integrated approach combining DFT and AIMD simulations was carried out to unravel the structure, dynamics, stability, and nature of host–guest interactions in hybrid assemblies. Geometry optimizations show that the triangular pores of NU-1000 and PCN-222-Zn and the diamond pores of MOF-177 adequately accommodate [Dy(Cp*)₂]⁺ without perturbing its local structure. Charge difference density and energy decomposition analysis reveal strong dispersion-driven host–guest interactions as the key stabilizing factor. CASSCF-SO-computed ab initio blockade barriers for all three [Dy(Cp*)₂]⁺@MOFs models show a giant barrier >1200 cm^–1, which is on par with [Dy(Cp*)₂]⁺. CASSCF-SO calculations on the AIMD trajectories of [Dy(Cp*)₂]⁺@NU-1000 (1–16 ps) reveal that the structural and magnetic properties remain unchanged post-encapsulation. Spin–vibronic analysis shows that the strongest spin-vibronic mode is attenuated by ∼30% upon encapsulation. Overall, our findings establish mesoporous MOFs as a promising avenue for stabilizing Ln-based SIMs with reduced vibrational decoherence, enabling long-range ordering and scalable integration of SMMs for futuristic applications.