Hexametallic manganese clusters with bulky derivatised salicylaldoximes

The reaction of Mn(ClO4)(2)center dot 6H(2)O with Ph-saoH(2) (Ph-saoH(2) = 2-hydroxybenzophenone oxime) in MeCN in the presence of sodium propionate forms the complex [(Mn6O2)-O-III(Ph-sao)(6)(prop)(2)-(MeCN)2]center dot 5.27MeCN (1.5.27MeCN) (prop = propionate). Repeating the same reaction in EtOH produces the complex [(Mn6O2)-O-III(Ph-sao)(6)(prop)2(EtOH)(4)] (2). Complexes 1 and 2 may be considered as structural isomers, since they display the same metallic core but different coordination modes of the propionate ligands; bridging in 1 and terminal in 2. Performing similar reactions and switching from sodium propionate to sodium adamantane-carboxylate (NaO2C-ada) and sodium pivalate (Napiv) in the presence of NEt4OH yields the complexes [(Mn6O2)-O-III(Ph-sao)(6)(O2C-ada)(2)(MeOH)(4)] (3) and [(Mn6O2)-O-III(Ph-sao)(6)(piv)(2)(EtOH)(4)]center dot 0.5Et(2)O (4.0.5Et(2)O), respectively. All four complexes contain the same {(Mn3O)-O-III(Ph-sao)(3)} building block. Variable temperature magnetic susceptibility and magnetization studies show that all complexes possess an S = 4 ground-state.