Stereoisomeric coordination polymers based on facial and meridional six-coordinate dysprosium(iii )

Due to the small differences in the chemical properties of facial (fac) and meridional (mer) stereoisomers, selective synthesis of one of the isomers is challenging, especially for lanthanide complexes. By using a flexible bidentate phosphine oxide ligand, we managed to isolate three stereoisomeric 2D and 3D coordination polymers, in which six-coordinate Dy(iii) ions possess fac- or mer-Cl3O3 coordination environments. Structural studies indicate that the stereochemistry differences result from their various supramolecular interactions (e.g., hydrogen bonding and pi MIDLINE HORIZONTAL ELLIPSIS pi stacking). Magnetic property measurements reveal the different static and dynamic magnetic behaviours of the three stereoisomers. Ab initio CASSCF calculations were then performed which indicated that their distinct magnetic behaviours arise from their fac/mer configurations. Compared to fac-Dy(iii), mer-Dy(iii) possesses more axial ground-state KDs and higher first excited KDs.

Automated summary

By using a flexible bidentate phosphine oxide ligand, three stereoisomeric coordination polymers with different coordination environments of Dy (III) ions were successfully isolated. Magnetic property measurements and calculations indicated distinct magnetic behaviors arising from their fac/mer configurations. Comparing fac-Dy (III) to mer-Dy (III), mer-Dy (III) possesses more axial ground-state KDs and higher first excited KDs.