Solvent responsive magnets comprise a class of molecule-based materials where lattice solvent driven structural transformation leads to the switching of magnetic properties. Herein, we present a special type of magnet where single-crystal to single-crystal (SCSC) transformations within mononuclear Dy^III compounds result in the switching of Dy^III single-molecule magnets (SMMs). This structural transformation involves lattice solvents which leads to significant changes in the color and magnetic properties. Additionally, the relaxation dynamics of mononuclear Dy^III compounds are perceptibly fine-tuned by the modification of β-diketonate ligands. The uniaxial magnetic anisotropies, magneto-structural correlations and the relaxation mechanism were investigated by magnetic studies and ab initio calculations. These experimental and theoretical studies indicate that compound 2 exhibits the best magnetic properties in compounds 1–4. The experimental observation is supported by the theoretical prediction of QTM time (τ^Zee_QTM) as theτ^Zee_QTM of 2 is remarkably longer than those of the other three compounds by an order of magnitude. This means that, compared with 1, 3, and 4, the magnetic relaxation of 2 is significantly slower. Meanwhile, 2 has the largest value of axial ESP (the axial electrostatic potential), which supports the smallest g_XY value in these compounds, resulting in better SMM properties. The present results offer a systematic synthesis regulation to change the magnetization dynamics and further understand magneto-structural correlations for Dy^III SMMs.