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Synthesis and Characterization of Symmetrically versus Unsymmetrically Proton-Bridged Hexa-Iron Clusters.

ABSTRACT: Syntheses and magnetic and structural characterization of hexa-iron complexes of derivatized salicylaldoximes are discussed. Complexation of Fe(BF₄)₂·6H₂O with each ligand (H₂ L1 and H₄ L2) in a methanolic-pyridine solution resulted in hexa-iron compounds (C1 and C2, respectively), which each contain two near-parallel metal triangles of [Fe₃-μ₃-O], linked by six fluoride bridges and stabilized by a hydrogen-bonded proton between the μ₃-O groups. Within each metal triangle of C2, Fe(III) ions are connected via the amine "straps" of (H₄ L2-2H). Variable-temperature magnetic susceptibility and Mössbauer data of C1 and C2 indicate the presence of dominant antiferromagnetic interactions between the high-spin (S = 5/2) Fe(III) centers. For C1, two quadrupole doublets are observed at room temperature and 5 K, consistent with structural data from which discrete but disordered [Fe₃-μ₃-O] and [Fe₃-μ₃-OH] species were inferred. For C2, a single sharp quadrupole doublet with splitting intermediate between those determined for C1 was observed, consistent with the symmetric [Fe₃-μ₃-O···H···μ₃-O-Fe₃] species inferred crystallographically from the very short μ₃-O···μ₃-O separation. The differences in the physical properties of the complexes, as seen in the Mössbauer, X-ray, and magnetic data, are attributed to the conformational flexibility imparted by the nature of the linkages between the closely related ligands.

SUBMITTER: De Silva DNT

PROVIDER: S-EPMC8246689 | biostudies-literature |

REPOSITORIES: biostudies-literature

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