Unusual Structural Types in Polynuclear Iron Chemistry from the Use of <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-Tetrakis(2-hydroxyethyl)ethylenediamine (edteH₄): Fe₅, Fe₆, and Fe₁₂ Clusters

The syntheses, crystal structures, and magnetochemical characterization of five new iron clusters [Fe5O2(O2CPh)7(edte)(H2O)] (1), [Fe6O2(O2CBut)8(edteH)2] (2), [Fe12O4(OH)2(O2CMe)6(edte)4(H2O)2](ClO4)4 (3), [Fe12O4(OH)8(edte)4(H2O)2](ClO4)4 (4), and [Fe12O4(OH)8(edte)4(H2O)2](NO3)4 (5) (edteH4 = N,N,N′,N′-tetrakis(2-hydroxyethyl) ethylenediamine) are reported. The reaction of edteH4 with [Fe3O(O2CPh)6(H2O)3](NO3) and [Fe3O(O2CBut)6(H2O)3](OH) gave 1 and 2, respectively. Complex 3 was obtained from the reaction of edteH4 and NaO2CMe with Fe(ClO4)3, whereas 4 and 5 were obtained from the reaction of edteH4 with Fe(ClO4)3 and Fe(NO3)3, respectively. The core of 1 consists of a [Fe4(μ3-O)2]8+ butterfly unit to which is attached a fifth Fe atom by four bridging O atoms. The core of 2 consists of two triangular [Fe3(μ3-O)]7+ units linked together by six bridging O atoms. Finally, the cores of 3−5 consist of an [Fe12(μ4-O)4(μ-OH)2]26+ unit. Variable-temperature (T) and -field (H) solid-state direct and alternating current magnetization (M) studies were carried out on complexes 1−3 in the 1.8–300 K range. Analysis of the obtained data revealed that 1, 2, and 3−5 possess an S = 5/2, 5, and 0 ground-state spin, respectively. The fitting of the obtained M/NμB vs H/T data was carried out by matrix diagonalization, and this gave values for the axial zero-field splitting (ZFS) parameter D of −0.50 cm−1 for 1 and –0.28 cm−1 for 2.