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

D. Nirosha T. De Silva, Tyson N. Dais, Geoffrey B. Jameson, Daniel J. Cutler, Euan K. Brechin, Casey G. Davies, Guy N. L. Jameson, Paul G. Plieger

Research output: Contribution to journalArticlepeer-review

Abstract / Description of output

Syntheses and magnetic and structural characterization of hexa-iron complexes of derivatized salicylaldoximes are discussed. Complexation of Fe(BF4)2·6H2O with each ligand (H2L1 and H4L2) 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 (H4L2-2H). 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.
Original languageEnglish
Pages (from-to)16661–16669
JournalACS Omega
Issue number25
Early online date15 Jun 2021
Publication statusE-pub ahead of print - 15 Jun 2021


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