Thermally Persistent High-Spin Ground States in Octahedral Iron Clusters

Abstract

Chemical oxidation and reduction of the all-ferrous (^HL)₂Fe₆ in THF affords isostructural, coordinatively unsaturated clusters of the type [(^HL)₂Fe₆] ⁿ: [(^HL)₂Fe₆][BArF₂₄] (1, n = +1; where [BArF₂₄]^- = tetrakis[(3,5-trifluoromethyl)phenyl]borate), [Bu₄N][(^HL)₂Fe₆] (2a, n = -1), [P][(^HL)₂Fe₆] (2b, n = -1; where [P]⁺ = tributyl(1,3-dioxolan-2-ylmethyl)phosphonium), and [Bu₄N]₂[(^HL)₂Fe₆] (3, n = -2). Each member of the redox-transfer series was characterized by zero-field ⁵⁷Fe Mössbauer spectroscopy, near-infrared spectroscopy, single-crystal X-ray crystallography, and magnetometry. Redox-directed trends are observed when comparing the structural metrics within the [Fe₆] core. The metal octahedron [Fe₆] decreases marginally in volume as the molecular reduction state increases as gauged by the Fe-Fe_avg distance varying from 2.608(11) Å ( n = +1) to 2.573(3) ( n = -2). In contrast, the mean Fe-N distances and ∠Fe-N-Fe angles correlate linearly with the [Fe₆] oxidation level, or alternatively, the changes observed within the local Fe-N₄ coordination planes vary linearly with the aggregate spin ground state. In general, as the spin ground state ( S) increases, the Fe-N(H)_avg distances also increase. The structural metric perturbations within the [Fe₆] core and measured spin ground states were rationalized extending the previously proposed molecular orbital diagram derived for (^HL)₂Fe₆. Chemical reduction of the (^HL)₂Fe₆ cluster results in an abrupt increase in spin ground state from S = 6 for the all-ferrous cluster, to S = ¹⁹/₂ in the monoanionic 2b and S = 11 for the dianionic 3. The observation of asymmetric intervalence charge transfer bands in 3 provides further evidence of the fully delocalized ground state observed by ⁵⁷Fe Mössbauer spectroscopy for all species examined (1-3). For each of the clusters examined within the electron-transfer series, the observed spin ground states thermally persist to 300 K. In particular, the S = 11 in dianionic 3 and S = ¹⁹/₂ in the monoanionic 2b represent the highest spin ground states isolated up to room temperature known to date. The increase in spin ground state results from population of the antibonding orbital band comprised of the Fe-N σ* interactions. As such, the thermally persistent ground states arise from population of the resultant single spin manifolds in accordance with Hund's rules. The large spin ground states, indicative of strong ferromagnetic electronic alignment of the valence electrons, result from strong direct exchange electronic coupling mediated by Fe-Fe orbital overlap within the [Fe₆] cores, equivalent to a strong double exchange magnetic coupling B for 3 that was calculated to be 309 cm^-1.