Slowing magnetic relaxation with open-shell diluents

Strategies for slowing magnetic relaxation via local environmental design are vital for developing next-generation spin-based technologies (e.g., quantum information processing). Herein, we demonstrate a technique to do so via chemical design of a local magnetic environment. We show that embedding the open-shell complex (Ph(4)P)(2)[Co(SPh)(4)] in solid-state matrices of the isostructural, open-shell species (Ph(4)P)(2)[M(SPh)(4)] (M = Ni(2+), S = 1; M = Fe(2+), S = 2; M = Mn(2+), [Formula: see text]) will slow magnetic relaxation for the embedded [Co(SPh)(4)](2−) ion by three orders of magnitude. Magnetometry, electron paramagnetic resonance (EPR), and computational analyses reveal that integer spin and large, positive zero-field splitting (D) values for the diluent produce a quiet, local magnetic field that slows relaxation rates for the embedded Co molecules. These results will enable the investigation of magnetic systems for which strictly diamagnetic congeners are either synthetically inaccessible or are not isostructural.