Slow magnetic relaxation in a family of trigonal pyramidal iron(II) pyrrolide complexes

We present a family of trigonal pyramidal iron(II) complexes supported by tris(pyrrolyl-α-methyl)amine ligands of the general formula [M(solv)(n)][(tpa(R))Fe] (M = Na, R = tert-butyl (1), phenyl (4); M = K, R = mesityl (2), 2,4,6-triisopropylphenyl (3), 2,6-difluorophenyl (5)) and their characterization by X-ray crystallography, Mössbauer spectroscopy, and high-field EPR spectroscopy. Expanding on the discovery of slow magnetic relaxation in the recently reported mesityl derivative 2, this homologous series of high-spin iron(II) complexes enables an initial probe of how the ligand field influences the static and dynamic magnetic behavior. Magnetization experiments reveal large, uniaxial zero-field splitting parameters of D = -48, -44, -30, -26, and -6.2 cm(-1) for 1-5, respectively, demonstrating that the strength of axial magnetic anisotropy scales with increasing ligand field strength at the iron(II) center. In the case of 2,6-difluorophenyl substituted 5, high-field EPR experiments provide an independent determination of the zero-field splitting parameter (D = -4.397(9) cm(-1)) that is in reasonable agreement with that obtained from fits to magnetization data. Ac magnetic susceptibility measurements indicate field-dependent, thermally activated spin reversal barriers in complexes 1, 2, and 4 of U(eff) = 65, 42, and 25 cm(-1), respectively, with the barrier of 1 constituting the highest relaxation barrier yet observed for a mononuclear transition metal complex. In addition, in the case of 1, the large range of temperatures in which slow relaxation is observed has enabled us to fit the entire Arrhenius curve simultaneously to three distinct relaxation processes. Finally, zero-field Mössbauer spectra collected for 1 and 4 also reveal the presence of slow magnetic relaxation, with two independent relaxation barriers in 4 corresponding to the barrier obtained from ac susceptibility data and to the 3D energy gap between the M(S) = ±2 and ±1 levels, respectively.