The reaction of 2-hydroxy-1, 4-naphthoquinone (Lawsone; Lw) and 3-methyl-2-hydroxy-1, 4-naphthoquinone (Phthiocol; Phth) with anhydrous CuCl2 results in [Cu(Lw)2(NH3)2] (M-1) and [Cu(Phth)2(NH3)].2H2O (M-2) complexes respectively. Thermal, magnetostructural and electrochemical studies indicate the polymeric nature of both the complexes. The energy of activations calculated from the thermogramms is found to be 65 kJ/Lw, 23.75 kJ/NH3 in M-1 and 178.90 kJ/H2O, 221.5 kJ/NH3, 566.2 kJ/Phth and 28.19 kJ/Phth in M-2. The increasing and decreasing nature of χm.T with decrease in temperature in M-1 and M-2 reveals the ferro and antiferromagnetic interactions in M-1 and M-2 respectively. The cyclic voltammetry studies indicate occurrence of effective metal ligand interactions in solution for both the complexes.