Bulking up: Hexanuclear oximato Fe(III) complexes surrounded by sterically demanding co-ligands

• Two novel hexanuclear oximato ferric cages were built using bulky co-ligands.
• The self-assembly of a related ferric tetranuclear cubane is also presented.
• Magnetic exchange within both cage types has been elucidated.

Despite their inherent steric bulk, a combination of 2-hydroxy-1-naphthaldoxime (L1H2) with polyphenolic carboxylate ligands (1-Naphthoate, 9-Anthracene carboxylate) aid the construction and stabilisation of hexanuclear arrays of Fe(III) ions in the form of [Fe(III)6O2(L1)2(O2C–R)10(H2O)2]·8MeCN (R = Naphth-(C10H8) (1); R = Anthra-(C14H9) (2)). Likewise, the sterically hindered ligand 3,5-di-tert-butyl-salicylaldoxime (L2H2) is able to aid the self-assembly of the tetranuclear, cubane-like species [Fe(III)4(L2)4(MeOH)4(Cl)4] (3). Magnetic susceptibility studies carried out on 1 and 3 reveal antiferromagnetic exchange between the Fe(III) metal centres affording S = 0 ground spin states in both cases.

Bulking up: sterically demanding oxime and carboxylate ligands combine to aid the self-assembly of hexanuclear [Fe6] cages. Magnetic susceptibility measurements reveal dominant antiferromagnetic exchange between the Fe(III) centres.Figure optionsDownload as PowerPoint slide