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The reaction of Cu(ClO 4 ) 2 · 6H 2 O and Cd(ClO 4 ) 2 with di-(2-picolyl)sulfur (dps) leads to the formation of mononuclear complexes [Cu(dps)(H 2 O)(ClO 4 )](ClO 4 ) (1) and [Cd(dps) 2 ](ClO 4 ) 2 (2). The crystal structure of 1 exhibits a distorted square pyramidal geometry, coordinated by one sulfur and two nitrogen atoms from the dps ligand, one water molecule and one perchlorate oxygen atom. For 2, the environment around cadmium atom is in a distorted octahedron with four nitrogen and two sulfur atoms from the dps ligand. Cyclic voltammetric data show that complexes undergo two waves of a one-electron transfer corresponding to M(II)/M(III) and M(II)/M(I) processes. Spectral and electrochemical behaviors of the complexes are also discussed.

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The reaction of CuCl 2 AE 2H 2 O and CdCl 2 with di-(2-picolyl)sulfide (dps) leads to the formation of mononuclear copper(II) and binuclear cadmium(II) complexes, [Cu(dps)Cl 2 ] AE H 2 O (1) and [(dps)(Cl)Cd II (l-Cl) 2 Cd II (Cl)(dps)](2). The copper atom in (1) is coordinated to one sulfur and two nitrogen atoms from the dps ligand and two chlorides in a distorted square-pyramidal environment. Complex (2) has two distorted octahedra sharing the basal edge that contain the bridging chloro ligands, each of which resides at a center of inversion. Cyclic voltammetric data show that (1) undergoes two reversible one-electron waves corresponding to Cu II /Cu III and Cu II /Cu I processes. However, cyclic voltammetry of (2) gives two irreversible reduced waves.

The reaction of [Cu(L)](ClO 4 ) 2 AE H 2 O (L ¼ 1, 3,10,12,16,19-hexaazatetracyclo[17,3,1,1 12.16 ,0 4.9 ]tetracosane) with NaN 3 and Na 2 tp yields mononuclear and dinuclear copper(II) complexes, [Cu(L)(N 3 )](ClO 4 ) (1) and [Cu(L)(ltp)](ClO 4 ) AE 2H 2 O (2). These complexes have been characterized by X-ray crystallography, electronic absorption, cyclic voltammetry and magnetic susceptibility. The crystal structure of (1) shows that the copper(II) ion has a distorted square-pyramidal geometry with the two secondary and two tertiary amines of the macrocycle and one nitrogen atom from the azide group coordinating the axial position. The copper(II) ions in (2) are bridged by the terephthalate anion to form a dinuclear complex, in which each copper(II) ion reveals a distorted square-pyramid with four nitrogen atoms of the macrocycle and the oxygen atom of bridging tp ligand. Cyclic voltammetry of the complexes gives two one-electron waves corresponding to Cu II /Cu III and Cu II /Cu I processes. The magnetic susceptibility measurement for (2) exhibits a weak antiferromagnetic interaction between copper(II) centers with a 2J value of )2.21 cm )1 (H ¼ )2JSS 1 AE S 2 ). The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature of the organic ligands.