Octanuclearity and tetradecanuclearity in manganese chemistry: an octanuclear manganese(II)/(III) complex featuring the novel [Mn8(mu4-O)2(mu3-OH)2]14+ core and [Mn10(II)Mn4(III)O4(O2CMe)20[(2-py)2C(OH)O]4] (2-py = 2-pyridyl).

Reactions of Mn sources with di-2-pyridyl ketone, (2-py)2CO, and phenyl 2-pyridyl ketone oxime, (ph)(2-py)CNOH, give the novel clusters [Mn10(II)Mn4(III)O4(O2CMe)20[(2-py)2C(OH)O]4] 1 and [Mn4(II)Mn4(III)O2(OH)2(O2CPh)10[(ph)(2-py)CNO]4] 2, respectively, which possess low-spin ground states; the observed tetradecanuclearity in 1 is extremely rare in 3d-metal chemistry, while the core of 2 has a unique topology consisting of two linked [Mn2(II)Mn2(III)O(OH)] units.