The synthesis of a penta(1-methylpyrazole)ferrocenyl phosphine oxide ligand (1) [Fe(C-5(C3H2N2CH3)(5))(C5H4PO(t-C4H9)(2))] is reported together with its X-ray crystal structure. Its self-assembly behavior with a dirhodium(II) tetraoctanoate linker (2) [Rh-2(O2CC7H15)(4)] was investigated for construction of fullerene-like assemblies of composition [(ligand)(12)(linker)(30)]. Reaction between 1 and 2 in acetonitrile resulted in the formation of a light purple precipitate (3). Evidence for the ligand-to-linker ratio of 1:2.5 expected for a fullerene-like structure [Fe(C-5(C3H2N2CH3)(5))(C5H4PO(t-C4H9)(2))](12)[Rh-2(O2CC7H15)(4)](30) was obtained from H-1 NMR and elemental analysis. IR and Raman studies confirmed the diaxially bound coordination environment of the dirhodium linker by comparing the stretching frequencies of the carboxylate group and the rhodium-rhodium bond with those in model compound (5), [Rh-2(O2CC7H15)(4)](C3H3N2CH3)(2)., the bis-adduct of linker 2 with 1-methylpyrazole. X-ray powder diffraction and molecular modeling studies provide additional support for the formation of a spherical molecule topologically identical to fullerene with a diameter of approximately 38 angstrom and a molecular formula of [(1)(12)(2)(30)]. Dissolution of 3 in tetrahydrofuran (THF) followed by layering with acetonitrile afforded purple crystals of [(1)(2)(2)](infinity) (6) [Fe(C-5(C3H2N2CH3)(5))(C5H4PO(t-C4H9)(2))] [Rh-2(O2CC7H15)(4)](2) with a two-dimensional polymeric structure determined by X-ray crystallography. The dirhodium linkers link ferrocenyl units by coordination to the pyrazoles but only four of the five pyrazole moieties of the pentapyrazole ligand are coordinated. The ligand-to-linker ratio of 1:2 in 6 was confirmed by H-1 NMR spectroscopy and elemental analyis, while results from IR and Raman are in agreement with the diaxially coordinated environment of the linker observed in the solid state.