Manganese–Salicyloximate Clusters Starting from [Mn^II(hfacac)₂]: From Mn₄ to Mn₁₂

Abstract The systematic exploration of the reactivity of [Mn(hfacac) 2 ] with R‐salicyloximes (R‐saloxH 2 : R = H, Me, Et) yielded a family of clusters with nuclearities ranging from Mn 4 to Mn 12 . The compounds with formula [Mn 6 (O) 2 (salox) 6 (CF 3 COO) 2 (EtOH) 4 ] ( 1 ) and [Mn 12 (salox) 12 (O) 4 (N 3 ) 4 (H 2 O) 2 (MeOH) 6 ] ( 4 ) show two or four linked {Mn(µ 3 ‐O)(salox) 3 } + triangular subunits. Magnetic measurements revealed spin ground states of S = 4 for 1 and S = 8 for 4 , as well as single‐molecule magnet responses and magnetic hysteresis above 2 K. The cubic [Mn 4 (Mesalox) 4 (MesaloxH) 4 ] ( 2 ), the hexanuclear [Mn 6 (Etsalox) 6 (O) 2 (MeO) 4 (MeOH) 2 ] ( 3 ) and the octanuclear [Mn 8 (Mesalox) 6 (O) 2 (N 3 ) 6 (MeOH) 8 ] ( 5 ) are polymorphs of previously reported systems. Small structural changes allows an S = 11 ground state for 3 .