First structurally characterized tricyanomanganate(III) and its magnetic {Mn(III)(2)M(II)(2)} complexes (M(II) = Mn, Ni).

Treatment of tris(3-cyano-2,4-pentanedionato)manganese(III) with KTp*, followed by [NEt(4)]CN affords [NEt(4)][(Tp*)Mn(III)(CN)(3)] (1); subsequent treatment of 1 with divalent triflates (OTf) and 2,2'-bipyridine (bpy) affords {Mn(III)(2)M(II)(2)} complexes (M(II) = Mn, 2; Ni, 3). Magnetic measurements show that 1-3 exhibit S(T) = 1, 3, and 4 spin ground states, respectively.