UC Berkeley

We report the synthesis and characterization of the trinuclear 4d-4f compounds [Co(C₅Me₅)₂][(C₅Me₅)₂Ln(μ-S)₂Mo(μ-S)₂Ln(C₅Me₅)₂], 1-Ln (Ln = Y, Gd, Tb, Dy), containing the highly polarizable MoS₄^3- bridging unit. UV-Vis-NIR diffuse reflectance spectra and DFT calculations of 1-Ln reveal a low-energy metal-to-metal charge transfer transition assigned to charge transfer from the singly occupied 4d_z² orbital of Mo^V to the empty 5d orbitals of the lanthanides (4d in the case of 1-Y), mediated by sulfur-based 3p orbitals. Electron paramagnetic resonance spectra collected for 1-Y in a tetrahydrofuran solution show large ⁸⁹Y hyperfine coupling constants of A_⊥ = 23 MHz and A_|| = 26 MHz, indicating the presence of significant yttrium-localized unpaired electron density. Magnetic susceptibility data support similar electron delocalization and ferromagnetic Ln-Mo exchange for 1-Gd, 1-Tb, and 1-Dy. This ferromagnetic exchange gives rise to an S = 15/2 ground state for 1-Gd and one of the largest magnetic exchange constants involving Gd^III observed to date, with J_Gd-Mo = +16.1(2) cm^-1. Additional characterization of 1-Tb and 1-Dy by ac magnetic susceptibility measurements reveals that both compounds exhibit slow magnetic relaxation. Although a Raman magnetic relaxation process is dominant for both 1-Tb and 1-Dy, an extracted thermal relaxation barrier of U_eff = 68 cm^-1 for 1-Dy is the largest yet reported for a complex containing a paramagnetic 4d metal center. Together, these results provide a potentially generalizable route to enhanced nd-4f magnetic exchange, revealing opportunities for the design of new nd-4f single-molecule magnets and bulk magnetic materials.