AbstractThe preparation and ligating properties of S‐oxygenated derivatives of a macrobinucleating hexaazadithiophenolate macrocycle H2L1 of the Robson type towards nickel(II) and zinc(II) ions are reported. Nickel complexes of the hexaazadiphenylsulfonate ligand (L2)2− [(L2)NiII2(μ‐L)]+ (L = m‐Cl‐OBz− (3), Cl− (4) and OAc− (6)] are readily obtained in high yields by oxidation of the respective [(L1)NiII2(μ‐L)]+ parent complexes [L = m‐Cl‐OBz− (2), Cl− (1), OAc− (5)] with meta‐chloroperoxybenzoic acid or hydrogen peroxide. Decomposition of the sulfonate complexes gives the free macrocycle H2L2 which, upon treatment with Zn(OAc)2·2H2O, produces the diamagnetic zinc complex [(L2)ZnII2(OAc)]+ (8). A dinuclear CuII complex of the hexaazadisulfinate derivative (L3′)2−, [(L3)CuII2]2+ (9), is formed rather unexpectedly by air oxidation of (L1)2− in the presence of CuI. The crystal‐structure determinations of the perchlorate or tetraphenylborate salts of 2, 3, and 4 show that the new ligands support the formation of binuclear complexes with bowl‐shaped, calixarene‐like binding cavities. NMR spectroscopic studies of 8 show that the complexes retain their solid‐state structures in solution. A crystal‐structure determination of 9 reveals two five‐coordinate CuII ions bridged by the two sulfinate functions of (L3)2−. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)