Abstract
Water reorientation is essential in a wide range of chemical and biological processes. However, the effects of such reorientation through rotation around the metal–oxygen bond on the chemical and physical properties of the resulting complex are usually ignored. Most studies focus on the donor property of water as a recognized σ donor-type ligand rather than a participant in the π interaction. Although a theoretical approach to study water-rotation effects on the functionality of a complex has recently been conducted, it has not been experimentally demonstrated. In this study, we determine that the magnetic anisotropy of a Co(II) complex can be effectively controlled by the slight rotation of coordinating water ligands, which is achieved by a two-step structural phase transition. When the water molecule is rotated by 21.2 ± 0.2° around the Co–O bond, the directional magnetic susceptibility of the single crystal changes by approximately 30% along the a-axis due to the rotation of the magnetic anisotropy axis through the modification of the π interaction between cobalt(II) and the water ligand. The theoretical calculations further support the hypothesis that the reorientation of water molecules is a key factor contributing to the magnetic anisotropy transition of this complex.
Highlights
Water reorientation is essential in a wide range of chemical and biological processes
Most studies focus on the coordination polyhedron and bond order of metal–oxygen bonds related to water ligands to elucidate the structure and properties of coordination complexes
This is because the donor property is typically assumed to be dominated by the σ donation rather than the π interaction in most low-valent transition metal complexes
Summary
Water reorientation is essential in a wide range of chemical and biological processes. We describe that a two-step rotational reorientation of a coordinated water molecule in a cobalt(II) complex results in a modification of the electronic structure, with the subsequent substantial changes in magnetic anisotropy.
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