Chiral All-Nitrogen-Coordinated Dysprosium Single-Molecule Magnets

Abstract

Two pairs of chiral end-on azido-bridged dinuclear hexaazamacrocycles, [Dy₂ (L^N6 _R/S )₂ (N₃ )₂ Cl₂ ](BPh₄ )₂ (1R/1S) and [Dy₂ (L^N6 _R/S )₂ (N₃ )₄ ]Cl₂ (2R/2S) (L^N6 _R/S is hexaazamacrocyclic neutral Schiff base ligand derived from 2,6-diformylpyridine and (1R, 2R)/(1S, 2S)-diaminocyclohexane), were constructed by adjusting the molar ratio of sodium azide to Dy(III) macrocycle precursor. Structural analyses reveal that all Dy(III) centers in complexes 1R/1S and 2R/2S are nine-coordinate with hula-loop coordination geometry, and the differences between 1R/1S and 2R/2S are the terminal coordination anion and counter anion. Magnetic studies indicate that complex 2S displays typical SMM behaviors under a zero dc field, whereas 1S just shows slow relaxation of magnetization resulting from a relatively weak axial crystal field. Significantly, complex 2R/2S represents the first homochiral all-nitrogen-coordinated lanthanide single-molecule magnet.

Keywords: all-nitrogen-coordinated; azide; enantiomer; macrocycle; single-molecule magnet.