Experimental and theoretical investigations on three DyIII4 single molecule magnets: structural and magneto-structural correlations

Abstract

The work in this report describes the syntheses, crystal structures, dc/ac magnetic behaviour, and theoretical calculations (both ab initio CASSCF and DFT) of three defect dicubane/planar butterfly type tetradysprosium(III) compounds of compositions [Dy^III₄L₄(μ₃-OH)₂(carboxylate)₂(dmf)₂] (carboxylate = formate (1), acetate (2), propionate (3)), where H₂L = 2-(2-hydroxy-3-ethoxybenzylideneamino)phenol. In the butterfly type structures, two Dy^III centres (Dy_b) occupy the body positions while two other (Dy_w) units occupy the wing positions. SHAPE analyses reveal that the coordination geometries of the Dy_b and Dy_w centres, both octacoordinated, are triangular dodecahedron (TDD) and square antiprism (SAPR), respectively. Variable-temperature magnetic susceptibility measurements give an indication of weak antiferromagnetic interactions and variable-field magnetization measurements reveal strong anisotropy in all the three compounds. The variable-temperature/frequency in-phase/out-of-phase AC susceptibility data reveal that all these three compounds are SMMs with two relaxation channels under zero dc field; slow relaxation (SR) and fast relaxation (FR) processes could be assigned to the SAPR (Dy_w) and TDD (Dy_b) metal centres, respectively. The simulated U_eff and τ₀ values are: 49.0 cm⁻¹ and 1.76 × 10^–7 s for 1, 30.3 cm⁻¹ and 1.51 × 10^–8 s for 2 and 23.4 cm⁻¹ and 9.64 × 10^–7 s for 3. Furthermore, ab initio CASSCF/RASSI-SO/SINGLE_ANISO calculations reveal that the ground state of Dy^III centres are axial in nature with a dominating contribution from m_J = |±15/2>. The magnetization relaxation occurs via the first excited KD resulting in the large computed blocking barrier of Dy_w (SAPR) centres compared to that of the Dy_b (TDD) centres which corroborates the experimental measurements. The exchange parameters obtained from DFT calculations are generally in line with those obtained from the fitting of χ_MT vs. T in POLY_ANISO calculations. Interesting structural and magneto-structural correlations have been found, which are the major outcomes of this investigation.