A New Tetradentate Mixed Aza-Thioether Macrocycle and Its Complexation Behavior towards Fe(II), Ni(II) and Cu(II) Ions

A new tetradentate mixed aza-thioether macrocyclic ligand 2,6-dithia[7](2,9)-1,10-phenanthrolinophane ([13]ane(phenN(2))S(2)) was successfully synthesized. Reacting metal precursors [Fe(CH(3)CN)(2)(OTf)(2)], Ni(ClO(4))(2)·6H(2)O, and Cu(ClO(4))(2)·6H(2)O with one equivalent of [13]ane(phenN(2))S(2) afforded [Fe([13]ane(phenN(2))S(2))(OTf)(2)] (1), [Ni([13]ane(phenN(2))S(2))](ClO(4))(2) (2(ClO(4))(2)), and [Cu([13]ane(phenN(2))S(2))(OH(2))](ClO(4))(2) (3(ClO(4))(2)), respectively. The structures of [13]ane(phenN(2))S(2) and all of its metal complexes were investigated by X-ray crystallography. The [13]ane(phenN(2))S(2) was found to behave as a tetradentate ligand via its donor atoms N and S.