The reaction of manganese(III) Schiff bases of the type salen(2-) (N,N'-ethylenebis(salicylideneaminato)) with X-substituted (X = CH3, Cl) pyridinecarboxamide dicyanoferrite(III) [Fe(X-bpb)(CN)(2)](-) gave rise to a series of cyanide-bridged Mn6Fe6 molecular wheels, [Mn-III(salen)](6)[Fe-III(bpmb)(CN)(2)](6)center dot 7H(2)O (1), [Mn(salen)](6)[Fe(bpClb)(CN)(2)](6)center dot 4H(2)O center dot 2CH(3)OH (2), [Mn(salen)](6)[Fe(bpdmb)(CN)(2)](6)center dot 10H(2)O center dot 5CH(3)OH (3), [Mn(5-Br(salpn))](6)[Fe(bpmb)(CN)(2)](6)center dot 24H(2)O center dot 8CH(3)CN (4), and [Mn(5-Cl(salpn))](6)[Fe(bpmb)(CN)(2)](6)center dot 25H(2)O center dot 5CH(3)CN (5). Compared with [Fe(bpb)(CN)(2)](-), which always gives rise to 1D or polynuclear species when reacting with Mn(III) Schiff bases, the introduction of substituents (X) to the bpb(2-) ligand has a driving force in formation of the novel wheel structure. Magnetic studies reveal that high-spin ground state S = 15 is present in the wheel compounds originated from the ferromagnetic Mn(III)-Fe(III) coupling. For the first time, the quantum Monte Carlo study has been used to modulate the magnetic susceptibility of the huge Mn6Fe6 metallomacrocycles, showing that the magnetic coupling constants J range from 3.0 to 8.0 K on the basis of the spin Hamiltonian H = -J(Sigma(i,j)s(Fei)S(Mnj) + s(Fe1)S(Mn12)). Hysteresis loops for 1 have been observed below 0.8 K, indicative of a single-molecule magnet with a blocking temperature (T-B) of 0.8 K. Molecular wheels 2-5 exhibit frequency dependence of alternating-current magnetic susceptibility under zero direct-current magnetic field, signifying the slow magnetization relaxation similar to that of 1. Significantly, an unprecedented archlike Mn2Fe2 cluster, [Mn(5-Cl(salpn))](2)[Fe(bpmb)(CN)(2)](2)center dot 3H(2)O center dot CH3CN (6), has been isolated as an intermediate of the Mn6Fe6 wheel 5. Ferromagnetic Mn(III)-Fe(III) coupling results in a high-spin S = 5 ground state. Combination of the high-spin state and a negative magnetic anisotropy (D) results in the observation of slow magnetization relaxation in 6.