Synthesis, crystal structures and magnetic properties of a series of chair-like heterometallic [Fe4Ln2] (Ln = GdIII, DyIII, HoIII, and ErIII) complexes with mixed organic ligands

Abstract

Four chair-like hexanuclear Fe–Ln complexes containing mixed organic ligands, namely, [Fe₄Ln₂{(py)₂CO₂}₄(pdm)₂(NO₃)₂(H₂O)₂Cl₄]·xCH₃CN·yH₂O (Ln = Gd^III (1, x = 1, y = 0), Dy^III (2, x = 1, y = 1), Ho^III (3, x = 0, y = 2), and Er^III (4, x = 1, y = 3); (py)₂CO₂H₂ = the gem-diol form of di-2-pyridyl ketone and pdmH₂ = 2,6-pyridinedimethanol) have been obtained by employing di-2-pyridyl ketone and 2,6-pyridinedimethanol reacting with FeCl₃ and Ln(NO₃)₃ in MeCN. The structures of 1–4 are similar to each other except for the number of lattice solvent molecules. Four Fe^III and two Ln^III in these complexes comprise a chair-like core with the “body” constructed by four Fe^III ions and the “end” constructed by two Ln^III ions. Among the four compounds, 2 shows field-induced single molecule magnet behavior as revealed by ac magnetic susceptibility studies, with the effective energy barrier and the pre-exponential factor of 22.07 K and 8.44 × 10⁻⁷ s, respectively. Ab initio calculations indicated that, among 2_Dy, 3_Ho and 4_Er fragments, the energy gap between the lowest two spin–orbit states for 2_Dy is the largest, while the tunneling gap for 2 is the smallest. These might be the reasons for complex 2 exhibiting SMM behavior. Additionally, the orientations of the magnetic anisotropy of Dy^III in 2 were obtained by electrostatic calculations and ab initio calculations, both indicating that the directions of the main magnetic axis of Dy1 ions are almost aligned along Dy1–O5 (O5 from the pdm²⁻ ligand).