Rare Nuclearities and Unprecedented Structural Motifs in Manganese Cluster Chemistry from the Combined Use of Di-2-Pyridyl Ketone with Selected Diols

The combined use of di-2-pyridyl ketone ((py)2CO) with various diols in Mn cluster chemistry has afforded five new compounds, namely, [Mn11O2(OH)2{(py)2CO2}5(pd)(MeCO2)3(N3)3(NO3)2(DMF)4](NO3)∙2DMF∙H2O (1∙2DMF∙H2O), [Mn11O2(OH)2{(py)2CO2}5(mpd)(MeCO2)3(N3)3(NO3)2(DMF)4](NO3) (2), [Mn12O4(OH)2{(py)2CO2}4(mpd)2(Me3CCO2)4(NO3)4(H2O)6](NO3)2∙2MeCN (3∙2MeCN), [Mn4(OMe)2{(py)2C(OMe)O}2(2-hp)2(NO3)2(DMF)2] (4), and [Mn7{(py)2CO2}4(2-hp)4(NO3)2(DMF)2](ClO4)∙DMF (5∙DMF) ((py)2CO22− (py)2C(OMe)O− = gem-diol hemiketal derivatives ketone, pdH2 1,3-propanediol, mpdH2 2-metly-1,3-propanediol, 2-hpH2 2-(hydroxymethyl)phenol). Complexes 1 2 are isostructural, possessing an asymmetric [MnIII5MnII6(μ4-O)(μ3-O)(μ3-OH)(μ-OH)(μ3-OR)2(μ-OR)10(μ-N3)]8+ core. Compound 3 is based on a multilayer [MnIII8MnII4(μ4-O)2(μ3-O)2(μ3-OH)2(μ-OR)12]10+ core, while complex 4 comprises defective dicubane crystal structure 5 reveals that it unusual non-planar [MnIII5MnII2(μ-OR)12]7+ core serpentine-like topology. Direct current (dc) magnetic susceptibility studies revealed the presence dominant antiferromagnetic exchange interactions 3, ferromagnetic coupling between ions was detected case compound 5. Fitting data for weak along peripheral MnII∙∙∙MnIII (Jwb −0.33 (1) cm−1) central MnIII∙∙∙MnIII (Jbb 6.28 cm−1).