Linear hexanuclear helical dysprosium single-molecule magnets: the effect of axial substitution on magnetic interactions and relaxation dynamics

Dalton Trans. 2019 Oct 7;48(37):14062-14068. doi: 10.1039/c9dt03101d. Epub 2019 Sep 6.

Abstract

The reaction between the rigid Schiff-base ligand H4L ([3,6-bis(2-hydroxy-3-methoxybenzylidene)hydrazinecarbonyl]-pyridazine) and different dysprosium(iii) salts afforded two new linear hexanuclear helical clusters, [Dy6L3(SCN)6(DMF)8]·4DMF (1), and [Dy6L3(NO3)6(DMF)4(H2O)2]·8DMF (2), which possess a similar Dy6 core with [Dy6L3(PhCOO)6(CH3OH)6]·11CH3OH·H2O (3). Modulation of the axial ligands around DyIII sites causes different coordination geometries and magnetic interactions, resulting in distinct magnetic relaxation behaviors. Compounds 1 and 2 show typical single-molecule magnet (SMM) properties with effective barriers (Ueff) of 15 and 68 K, respectively, which could greatly profit from strong ferromagnetic interactions compared with compound 3. Presence of a hula-hoop-like geometry of the DyIII ions and stronger ferromagnetic interactions results in better SMM performance of compound 2 than that of 1.