Magnetic anisotropy of two trinuclear and tetranuclear CrIIINiII cyanide-bridged complexes with spin ground states S = 4 and 5

Abstract

The trinuclear and the tetranuclear complexes [{iPrtacnCr(CN)₃}₂{Ni(cyclam)}](NO₃)₂·5H₂O 1 (cyclam = 1,4,8,11-tetraazacyclotetradecane, iPrtacn = 1,4,7-tris-isopropyl-1,4,7-triazacyclononane) and [{iPrtacnCr(CN)₃Ni(Me₂bpy)₂}₂](ClO₄)₄·2CH₃CN 2 (Me₂bpy = 4,4′-dimethyl-2,2′-bipyridine) were synthesized by reacting (iPrtacn)Cr(CN)₃ with [Ni(cyclam)](NO₃)₂ and [Ni(Me₂bpy)₂(H₂O)₂](ClO₄)₂,, respectively. The crystallographic structure of the two compounds was solved. The molecular structure of complex 1 consists of a linear Cr–Ni–Cr arrangement with a central Ni(cyclam) unit surrounded by two Cr(iPrtacn)(CN)₃ molecules through bridging cyanides. Each peripheral chromium complex has two pending CN ligands. Complex 2 has a square planar arrangement with the metal ions occupying the vertices of the square. Each Cr(iPrtacn)(CN)₃ molecule has two bridging and one non-bridging cyanide ligands. The magnetic properties of the two complexes were investigated by susceptibility vs. temperature and magnetization vs. field studies. As expected from the orthogonality of the magnetic orbitals between Cr^III (t_2g³) and Ni^II (e_g²) metal ions, a ferromagnetic exchange interaction occurs leading to a spin ground states S = 4 and 5 for 1 and 2, respectively. The magnetization vs. field studies at T = 2, 3 and 4 K showed the presence of a magnetic anisotropy within the ground spin states leading to zero-field splitting parameters obtained by fitting the data D₄ = 0.36 cm⁻¹ and D₅ = 0.19 cm⁻¹ (the indices 4 and 5 refer to the ground states of complexes 1 and 2, respectively). In order to quantify precisely the magnitude of the axial (D) and the rhombic (E) anisotropy parameters, High-field high frequency electron paramagnetic resonance (HF-HFEPR) experiments were carried out. The best simulation of the experimental spectra (at 190 and 285 GHz) gave the following parameters for 1: D₄ = 0.312 cm⁻¹, E₄/D₄ = 0.01, g_4x = 2.003, g_4y = 2.017 and g_4z = 2.015. For complex 2 two sets of parameters could be extracted from the EPR spectra because a doubling of the resonances were observed and assigned to the presence of complexes with slightly different structures at low temperature: D₅ = 0.154 (0.13) cm⁻¹, E₅/D₅ = 0.31 (0.31) cm⁻¹, g_4x = 2.04 (2.05), g_4y = 2.05 (2.05) and g_4z = 2.03 (2.02). The knowledge of the magnetic anisotropy parameters of the mononuclear Cr(iPrtacn)(CN)₃, Ni(cyclam)(NCS)₂ and Ni(bpy)₂(NCS)₂ complexes by combining HF-HFEPR studies and calculation using a software based on the angular overlap model (AOM) allowed to determine the orientation of the local D tensors of the metal ions forming the polynuclear complexes. We, subsequently, show that the anisotropy parameters of the polynuclear complexes computed from the projection of the local tensors are in excellent agreement with the experimental ones extracted from the EPR experiments.