A new family of heterometallic pentanuclear complexes of formulas [Mn(IV)Mn(2)(III)Ln(2)(III)O(2)(benz)(4)(mdea)(3)(NO3)(2)(MeOH)] (Ln = Dy (1-Dy), Tb (2-Tb), Gd (3-Gd), Eu (4-Eu), Sm (5-Sm), Nd (6-Nd), Pr (7-Pr); benz(H) = benzoic acid; mdeaH(2)= N-methyldiethanolamine) and [Mn(IV)Mn(2)(III)Ln(2)(III)O(2)(o-tol)(4)(mdea)(3)(NO3)(2)(MeOH)] (Ln = Gd (8-Gd), Eu (9-Eu); o-tol(H) = o-toluic acid) have been isolated and structurally, magnetically, and theoretically characterized. dc magnetic susceptibility measurements reveal dominant antiferromagnetic magnetic interactions for each complex, except for 2-Tb and 3-Gd, which reveal an upturn in the chi T-M product at low temperatures. The magnetic interactions between the spin centers in the Gd derivatives, 3-Gd and 8-Gd, which display markedly different chi T-M vs T profiles, were found to be due to the interactions of the Gd-III-Gd-III ions which change from ferromagnetic (3-Gd) to antiferromagnetic (8-Gd) due to structural differences. ac magnetic susceptibility measurements reveal a nonzero out-of-phase component for 1-Dy and 7-Pr, but no maxima were observed above 2 K (H-dc = 0 Oe), which suggests single-molecule magnet (SMM) behavior. Out-of-phase signals were observed for complexes 2-Tb, 4-Eu, 8-Gd, and 9-Eu, in the presence of a static dc field (H-dc = 2000, 3000 Oe). The anisotropic nature of the lanthanide ions in the benzoate series (1-Dy, 2-Tb, 5-Sm, 6-Nd, and 7-Pr) were thoroughly investigated using ab initio methods. CASSCF calculations predict that the origin of SMM behavior in 1-Dy and 7-Pr and the applied field SMM behavior in 2-Tb does not solely originate from the single-ion anisotropy of the lanthanide ions. To fully understand the relaxation mechanism, we have employed the Lines model to fit the susceptibility data using the POLY_ANISO program, which suggests that the zero-field SMM behavior observed in complexes 1-Dy and 7-Pr is due to weak Mn-III/IV-Ln(III) and Ln(III)-Ln(III) couplings and an unfavorable Ln(III)/Mn-III/Mn-IV anisotropy. In complexes 4-Eu, 8-Gd, and 9-Eu ab initio calculations indicate that the anisotropy of the Mn-III Cions solely gives rise to the possibility of SMM behavior. Complex 7-Pr is a Pr(III)-containing complex that displays zero-field SMM behavior, which is rare, and our study suggests the possibility of coupling weak SOC lanthanide metal ions to anisotropic transition-metal ions to derive SMM characteristics; however, enhancing the exchange coupling in {3d-4f} complexes is still a stubborn hurdle in harnessing new generation {3d-4f} SMMs.