Synthetic Factors Determining the Curvature and Nuclearity of the Giant Mn70 and Mn84 Clusters with a Torus Structure of ∼4 nm Diameter

New members of the Mn70 and Mn84 torus-like cluster family have been prepared from a hybrid comproportionation-alcoholysis reaction of [Mn12O12(O2CR)16(H2O)4] in alcohol in the presence of R'CO2H with NnBuMnO4 or MnII salts as initiators. Reactions using MeCO2H in nPrOH or nBuOH gave [Mn70O60(O2CMe)70(OnPr)20(nPrOH)18.5(H2O)21.5] (3) and [Mn70O60(O2CMe)70(OH)3(OnBu)17(nBuOH)7.5(H2O)32.5] (4), respectively, whereas EtCO2H in nPrOH gave [Mn84O72(O2CEt)84(OnPr)24(nPrOH)16(H2O)32] (5). They consist of alternating near-linear [Mn3(μ3-O)4]+ and distorted-cubane [Mn4(μ3-O)2(μ3-OR)2]6+ units bridged by syn,syn-μ-RCO2- and μ3-O2- groups and overall are [Mn14]5 and [Mn14]6 oligomers, the repeating unit containing two Mn3 and two Mn4 units. 3/4/5 possess external diameters (including organic ligands) of 4.0/4.1/4.6 nm, respectively, and crystallize as supramolecular nanotubes but with different packing arrangements. Considering all Mn70/Mn84 tori now available, we conclude that the Mn70 vs Mn84 nuclearity is determined by the relative bulk of the carboxylates vs the alkoxides, their increasing bulk favoring Mn84 and Mn70, respectively, with carboxylates larger than acetate giving Mn84. Alternating current (ac) magnetic susceptibility studies revealed frequency-dependent χ″M signals below ∼2.4 K, indicating 3-5 to be new members of the giant [Mn14]n torus family of giant single-molecule magnets (SMMs), in which Mn84 and Mn70 are the largest homometallic Mn/O clusters and SMMs to date.