Manganese-salicyloximate clusters stating from [MnII(hfacac)2]: from Mn4 to Mn12

Abstract

The systematic exploration of the reactivity of [Mn(hfacac)2] with R‐salicyloximes (R‐saloxH2: R = H, Me, Et) yielded a family of clusters with nuclearities ranging from Mn4 to Mn12. The compounds with formula [Mn6(O)2(salox)6(CF3COO)2(EtOH)4] (1 ) and [Mn12(salox)12(O)4(N3)4(H2O)2(MeOH)6] (4 ) show two or four linked {Mn(µ3‐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 [Mn4(Mesalox)4(MesaloxH)4] (2 ), the hexanuclear [Mn6(Etsalox)6(O)2(MeO)4(MeOH)2] (3 ) and the octanuclear [Mn8(Mesalox)6(O)2(N3)6(MeOH)8] (5 ) are polymorphs of previously reported systems. Small structural changes allows an S = 11 ground state for 3 .