Alcoholysis of preformed tetranuclear and hexanuclear iron(III) clusters has been employed for the synthesis of four higher-nuclearity clusters. Treatment of [Fe4O2(O2CMe)(7)(bpy)(2)](ClO4) with phenol affords the hexanuclear cluster [Fe6O3(O2CMe)(9)(OPh)(2)(bpy)(2)](ClO4) (1). Reaction of [Fe6O2(OH)(2)(O2CR)(10)(hep)(2)] (R = Bu-t or Ph) with PhOH affords the new "ferric wheel" complexes [Fe-8(OH)(4)(OPh)(8)(O2CR)(12)] [R = Bu-t (2) or Ph (3)]. Complexes 2 and 3 exhibit the same structure, which is an unprecedented type for Fe(III). In contrast, treatment of [Fe6O2(OH)(2)(O2CBut)(10)(hep)(2)] with MeOH leads to the formation of [Fe-10(OMe)(20)(O2CBut)(10)] (4), which exhibits the more common type of ferric wheel seen in analogous complexes with other carboxylate groups. Solid-state variable-temperature magnetic susceptibility measurements indicate spin-singlet ground states for complexes 2 and 4. The recently developed semiempirical method ZILSH was used to estimate the pairwise exchange parameters (J(AB)) and the average spin couplings (S) over cap (A).(S) over cap (B) between the Fe(III) centers, providing a clear depiction of the overall magnetic behavior of the molecules. All exchange interactions between adjacent Fe(III) atoms are antiferromagnetic.