[Mn₁₂O₁₂(OMe)₂(O₂CPh)₁₆(H₂O)₂]^2- Single-Molecule Magnets and Other Manganese Compounds from a Reductive Aggregation Procedure

A new synthetic procedure has been developed in Mn cluster chemistry involving reductive aggregation of permanganate (MnO4-) ions in MeOH in the presence of benzoic acid, and the first products from its use are described. The reductive aggregation of NBun4MnO4 in MeOH/benzoic acid gave the new 4MnIV, 8MnIII anion [Mn12O12(OMe)2(O2CPh)16(H2O)2]2-, which was isolated as a mixture of two crystal forms (NBun4)2[Mn12O12(OMe)2(O2CPh)16(H2O)2]·2H2O·4CH2Cl2 (1a) and (NBun4)2[Mn12O12(OMe)2(O2CPh)16(H2O)2]·2H2O·CH2Cl2 (1b). The anion of 1 contains a central [MnIV4(μ3-O)2(μ-O)2(μ-OMe)2]6+ unit surrounded by a nonplanar ring of eight MnIII atoms that are connected to the central Mn4 unit by eight bridging μ3-O2- ions. This compound is very similar to the well-known [Mn12O12(O2CR)16(H2O)4] complexes (hereafter called “normal Mn12”), with the main difference being the structure of the central cores. Longer reaction times (∼2 weeks) led to isolation of polymeric [Mn(OMe)(O2CPh)2]n (2), which contains a linear chain of repeating [MnIII(μ-O2CPh)2(μ-OMe)MnIII] units. The chains are parallel to each other and interact weakly through π-stacking between the benzoate rings. When KMnO4 was used instead of NBun4MnO4, two types of compounds were obtained, [Mn12O12(O2CPh)16(H2O)4] (3), a normal Mn12 complex, and [Mn4O2(O2CPh)8(MeOH)4]·2MeOH (4·2MeOH), a new member of the Mn4 butterfly family. The cyclic voltammogram of 1 exhibits three irreversible processes, two reductions and one oxidation. One-electron reduction of 1 by treatment with 1 equiv of I- in CH2Cl2 gave (NBun4)[Mn12O12(O2CPh)16(H2O)3]·6CH2Cl2 (5·6CH2Cl2), a normal Mn12 complex in a one-electron reduced state. The variable-temperature magnetic properties of 1, 2, and 5 were studied by both direct current (dc) and alternating current (ac) magnetic susceptibility measurements. Variable-temperature dc magnetic susceptibility studies revealed that (i) complex 1 possesses an S = 6 ground state, (ii) complex 2 contains antiferromagnetically coupled chains, and (iii) complex 5 is a typical [Mn12]- cluster with an S = 19/2 ground state. Variable-temperature ac susceptibility measurements suggested that 5 and both isomeric forms of 1 (1a,b) are single-molecule magnets (SMMs). This was confirmed by the observation of hysteresis loops in magnetization vs dc field scans. In addition, 1a,b, like normal Mn12 clusters, display both faster and slower relaxing magnetization dynamics that are assigned to the presence of Jahn−Teller isomerism.