Significantly Enhancing the Single-Molecule-Magnet Performance of a Dinuclear Dy(III) Complex by Utilizing an...

In this work, we employed an asymmetric auxiliary organic ligand (1,1,1-trifluoroacetylacetone, Htfac) to further regulate the magnetic relaxation behavior of series of Dy₂ single-molecule magnets (SMMs) with a N1,N3-bis(3-methoxysalicylidene)diethylenetriamine (H₂L) ligand. Fortunately, an air-stable Dy₂ complex, [Dy₂(L)₂(tfac)₂] (1; Htfac = 1,1,1-trifluoroacetylacetone) was obtained at room temperature. A structural analysis indicated that some Dy-O or Dy-N bond lengths for 1 are not in the range of those for the complexes [Dy^III₂(L)₂(acac)₂]·2CH₂Cl₂ (Dy-acac; Hacac = acetylacetone) and [Dy^III₂(L)₂(hfac)₂] (Dy-hfac; Hhfac = hexafluoroacetylacetone), although the electron-withdrawing ability of tfac^- is stronger than that of acac^- but weaker than that of hfac^-. Additionally, the Dy-O3/O3a (the two O atoms bridged to Dy^III ions) bond lengths are also affected by the asymmetrical Htfc ligand. This indicated that the charge distribution of the coordination atoms around Dy^III has been modified in 1, which leads to the fine-tuning of the magnetic relaxation behavior of 1. Magnetic studies indicated that the values of effective energy barrier (U_eff) for 1 and its diluted sample (2) are 234.8(3) and 188.0(6) K, respectively, which are both higher than the reported value of 110 K for the complex Dy-hfac. More interestingly, 1 exhibits a magnetic hysteresis opening when T < 2.5 K at zero field, while the hysteresis loops of 2 are closed at a zero dc field. This discrepancy is due to the weak intramolecular exchange coupling in 2, which cannot overcome the QTM of the single Dy^III ion. Ab initio calculations for 1 revealed that the charge distributions of the coordination atoms around Dy^III ions were regulated and the intramolecular exchange coupling was indeed improved when the asymmetrical Htfc was employed as a ligand for the synthesis of this kind of Dy₂ SMM.