Synthesis and characterization of copper(II) hexaazamacrotetracyclic complexes containing organic ligands

Two mononuclear copper(II) complexes [Cu(L)(NO^sub 2^)](ClO^sub 4^) (1) and [Cu(L)(MO^sub 4^)]^sub 2^· 5H^sub 2^O (2) (L = 1,3,10, 12,16,19-hexaazatetracyclo[17,3,1,1^sup 12.16^,0^sup 4.9^]tetracosane) have been synthesized and their structures determined. Both compounds show a distorted square-pyramidal geometry with the two secondary and two tertiary amines of the macrocycle and one ligand coordinated at the axial position. Cyclic voltammetry of the complexes gives two one-electron waves corresponding to Cu^sup II^/Cu^sup III^ and Cu^sup II^/Cu^sup I^ processes. The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature of the organic ligands.[PUBLICATION ABSTRACT]