The diverse chemistry of the earth abundant Fe ion remains at the forefront of a variety of transformative scientific disciplines, including biochemistry, catalysis, 2 porous materials, nanoparticles, batteries, superconductivity, thermoelectrics, spintronics, and magnetism. In the latter area Fe remains ubiquitous in both solid-state and molecule-based chemistry. The recent discoveries of three molecular iron oxide compounds, [Fe13], [Fe17], and [Fe34], with structures related to the minerals ferrihydrite and magnetite, suggests that several other very large, high symmetry, molecular clusters exist en route to the formation of 3D oxide or oxyhydroxide mineral phases. In turn, this hints that (large) lacunary or diminished molecular oxyhydroxide [FeO(OH)] clusters not conforming to mineral structure types, including heterometallic species, must also exist. The plausibility of this concept is further supported by the existence of the iron storage protein ferritin which holds ~4,500 Fe III ions in a molecular ferrihydrite cluster in the inner wall of its spherical shell. The synthetic procedures used to make [Fe13,], [Fe17,] and [Fe34] are remarkably straightforward. For example, [Fe17] is made by dissolving anhydrous FeBr3 in wet pyridine (py) (or from a combination of pyridine with a second co-solvent). [Fe34] comes from an analogous reaction to [Fe17] but with a different solvent ratio and in the presence of an additional base/templating agent. The wet pyridine acts as a solvent, a source of H2O (O 2-, OH -), base, ligand, and cation (pyH + ). Charge balancing anions originate from the salt employed. Interestingly, in the formation of the [Fe17] cage the py can be replaced with a number of different analogues, including 4-ethylpyridine, β-picoline, 3,5-lutidine, and isoquinoline, reflecting the relative stability of the compound.