Solvent Modification of the Structures and Magnetic Properties of a Series of Dysprosium(III) Single-Molecule Magnets.

Abstract

Solvent effects on the structures and magnetic properties of single-molecule magnets (SMMs) have been of great interest for modification of the SMMs using chemical modulation. By systematically varying the reaction solvents (MeOH, ethanol, n-propanol, and n-butanol), we have successfully synthesized a series of DyIII-H4daps complexes (H4daps = N',N‴-[(1E,1'E)-pyridine-2,6-diylbis(ethan-1-yl-1-ylidene)]bis(2-hydroxybenzohydrazide), including two binuclear compounds, [Dy2(H2daps)2(MeOH)4(H2O)2](CF3SO3)2·0.5MeOH (1MeOH) and [Dy2(H2daps)3(EtOH)2]·2EtOH·Et2O (2EtOH), and two mononuclear compounds, [Dy(H4daps)2](CF3SO3)3·n-PrOH (3PrOH) and [Dy(H4daps)(CF3SO3)3(n-BuOH)]·0.5Et2O (4BuOH). Using different solvents, the ligand-to-metal ratios can be adjusted from 1:1 in 1MeOH and 4BuOH to 3:2 in 2EtOH and 2:1 in 3PrOH. Through the solvent crossover experiments, the role of the solvents and the conditions to form these complexes were carefully studied. The size of the different alcohols, their coordination ability to the DyIII center, and the solubility of the complexes in these alcohols might affect the assembly process and lead to modification of the structures and magnetic properties of these DyIII-H4daps complexes. Magnetic studies revealed that these four complexes all exhibit slow magnetic relaxation under a zero or an applied direct-current field, with an energy barrier of about 100 K for the binuclear compound 1MeOH. In combination with theoretical calculations, the magnetic-structure relationship of these four compounds has been analyzed. This work demonstrates the crucial role of different solvent molecules in the fine-tuning of the structures and magnetic performances of different lanthanide complexes.