A Rare Example of Four-Coordinate Nonoxido Vanadium(IV) Alkoxide in the Solid State: Structure, Spectroscopy, and Magnetization Dynamics

The distorted tetrahedral [V(OAd)4] alkoxide (OAd = 1-adamantoxide, complex 1) is the first homoleptic, mononuclear vanadium(IV) alkoxide to be characterized in the solid state by X-ray diffraction analysis. The compound crystallizes in the cubic P43n space group with two highly disordered, crystallographically independent molecules in the asymmetric unit. Spin Hamiltonian parameters extracted from low temperature X- and Q-band electron paramagnetic resonance (EPR) experiments performed for polycrystalline samples of 1, both in the concentrated (bulk) form and diluted in the diamagnetic [Ti(OAd)4] analogue, reveal a fully axial system with gz < gx, gy and Az ≫ Ax, Ay. Complex 1 has also been characterized by alternate current susceptometry with varying temperature (3–30 K) and static magnetic field (up to 8.5 T), showing field-induced slow relaxation of the magnetization with relaxation times ranging from ca. 3 ms at 3 K to 0.02–0.03 ms at 30 K, in line with relevant results described recently for other ...