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Template condensation reactions of formaldehyde with appropriate tetramines and diamines in the presence of N(Ⅱ) or Cu(Ⅱ) ion produce square planar complexes of hexaaza macrotricyclic and macrotetracyclic ligands [M(L)]2+(M = Ni(Ⅱ) or Cu(Ⅱ); L = 4-methyl-1,3,6,8,11,14-hexaazatricyclo[12,2,1,18,11]octadecane(C), 1,3,10,12,15,18-hexaazatetracyclo[16,2,1,112,15,04,9]docosane(D) 4-methyl-1,3,6,8,12,15-hexaazatricyclo[13,3,1,18,12]eicosane(F), or 1,3,10,12,16,19-hexaazatetracyclo[l7,3,1,112,16,04,9]tetracosane(G). These complexes contain two 1,3-diazacyclopentane or 1,3-diazacyclohexane rings in the six-membered chelate rings. The complexes of C and F contain one methyl group and those of D and G one cyclohexane ring in the five-membered chelate ring. Synthesis and characterization of the Ni(Ⅱ) and Cu(Ⅱ) complexes are presented. The effects of the ligand structure on the equilibrium [Ni(L)]2+ ＋ 2H2O ↔ [Ni(L)(H2O)2]2+ in aqueous solutions are described.
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