Four mononuclear dysprosium complexes with neutral Schiff-base ligands: syntheses, crystal structures and slow magnetic relaxation behavior

Abstract

Four mononuclear 9-coordinate Dy-based complexes, [Dy(HL¹)₂(NO₃)₃(CH₃OH)] (1Dy), [Dy(HL²)₂(NO₃)₃(H₂O)] (2Dy), [Dy(HL³)₃(NO₃)₃]·CH₃CN (3Dy), and [Dy(HL⁴)₃(NO₃)₃] (4Dy), have been constructed by neutral Schiff-base ligands (1-[N-(4-R)aminomethylidene-2(1H)-naphthalenone, R = –Cl (HL¹), –NO₂ (HL²), –OCH₃ (HL³), –I (HL⁴)). By tuning the terminal substituent group of HL ligands, the number of HL ligands coordinated to the central Dy³⁺ ion unexpectedly varies from 2 to 3, and the local symmetry around the Dy³⁺ ion reduces from D_3h to C_s. Magnetic measurements reveal that 2Dy can display single-ion magnet (SIM) behavior in zero dc field, while 1Dy, 3Dy and 4Dy show field-induced slow magnetic relaxation. Ab initio calculations were employed to elucidate magnetic anisotropy in the complexes, including g-tensors, averaged transition magnetic moments and magnetic easy axes. The difference in magnetic behaviors of the four complexes can be ascribed to the terminal substituent effect of neutral Schiff-base ligands.