Polymetallic complexes of Fe III ion have always played a prominent role in the development molecular magnetism. [Fe dimers, [Fe triangles 2 and [Fe butterflies not only represented ideal systems for developing quantitative magneto-structural correlations, they were also employed synthetically as starting materials for constructing larger and more complex species. The latter often contain the same vertex-, edge-, face-sharing structural units as the reactants, linked via organic and inorganic bridging ligands. The large library of complexes produced therefrom allowed chemists to understand the processes by which larger clusters self-assemble, allowing some control over the resultant magnetic properties, targeting, for example, slow relaxation of the magnetisation, spin frustration, or an enhanced magnetocaloric effect. One interesting sub-set of species in this family are molecular iron oxides, an emerging class of materials whose structures, in the main, contain no bridging organic ligands and conform to mineral phases such as ferrihydrite and magnetite. As well as displaying fascinating magnetic behaviours, such species potentially have applications in a breadth of areas ranging from catalysis 9 and battery technologies 10 to biomedical imaging. The striking structural similarties between the molecular iron oxides [Fe III 13], 12 [Fe III 17], 8,13 [Fe III 30], 14 and [Fe 15 which all possess alternating "layers" or tetrahedral and octahedral Fe III ions has prompted us to speculate, and examine, whether very large molecular iron oxides, perhaps even rivalling the size and complexity of the polyoxometalates, 15 can be isolated. The inability of Fe III to be stabilised by terminal oxide ions and the propensity of aqueous solutions of Fe III to produce mixtures of intractable/insoluble/amorphous solids suggests however that alternative synthetic pathways may have to be explored. The simplicity of the synthesis of [Fe17] represents a good starting point. It is made by dissolving anhydrous FeBr3 in wet pyridine. The latter acts as solvent, base, source of oxide/hydroxide, terminal ligand and charge balancing counter cation (pyH + ). Analogous reactions replacing the pyridine with β-picoline, 4-ethylpyridine, isoquinolene, 3,4-lutidine, results in a series of isostructural species. Addition of different bases, templates and solvent combinations results in the formation of the related, but larger [Fe30] and [Fe34] clusters. Herein, we extend this methodology to the use of 4-methoxypyridine (MeO-py) and the synthesis of the smallest member of this molecular iron oxide family, an [Fe8] cage.