Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear MII3O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

Metal complexes of trithiadodecaazahexaphyrin (Hhp) that contain MII3O clusters inside a π-extended trianionic (Hhp3–) macrocycle have been prepared. Studies of the magnetic properties of NiII3O(Hhp) and CuII3O(Hhp) reveal a diamagnetic and EPR-silent trianionic (Hhp3–) macrocycle and diamagnetic NiII3(O2–) or paramagnetic CuII3(O2–) tetracations. The positive charge of MII3O(Hhp) is compensated by one acetate anion {MII3O(Hhp)}+(CH3CO2–). The...