Reaction of ZnII-acetate with two N, N, O-donor Schiff-base ligands, HL1 {4-Chloro-2-[(2-morpholin-4-yl-ethylimino)-methyl]- phenol} and HL2 {4-Chloro-2-[(3-morpholin-4-yl-propylimino)-methyl]- phenol}, which are formed in situ via condensation of 5-chlorosalicylaldehyde and N-(2-aminoethyl/propyl)morpholine, produce one tri- and one mononuclear species, Zn3L1(OAc)4 (1) and ZnL 2(OAc) (2). The hypothetical ZnL1(OAc) and Zn 3L2(OAc)4 are energetically unfavorable by 9.2 and 5.1 kcal/mol, in compare with their respective real counterparts 1 and 2 evidenced from DFT calculations. Both 1 and 2 catalyze the hydrolytic cleavage of phosphoester bond of (4-nitrophenyl) phosphate where 1 shows higher activity than that of 2. The proposed mechanistic pathways of phosphatase activity of 1 and 2 and the higher efficiency of the latter have been rationalized by DFT study. DNA cleavage activities have been investigated using supercoiled pET28a plasmid DNA where both the complexes show dose dependent DNA cleavage activity with varying degree. Complex 1 shows excellent breakage activity even at a concentration of 20 μM. However, in both cases hydroxyl radical pathway is most probably operative in DNA cleavage activity. © 2014 Elsevier B.V. All rights reserved.