The protonation constants of two nitro-Schiff bases SB 1 , SB 2 and three asymmetric tetradentate diimines H 2 L 1 , H 2 L 2 and H 2 L 3 and the stability constants of their ML type binuclear Ni(II) and Fe(III) complexes have been determined potentiometrically. The asymmetric diimines are (2OH) RACH‚NAC 6 H 4 ACH‚NAR 0 (2OH) type compounds [where R = R 0 = phenyl for H 2 L 1 ; R = naphthyl, R 0 = phenyl for H 2 L 2 and R = R 0 = naphthyl for H 2 L 3 ]. The effect of tautomeric forms on the acid-base properties of the diimines has been investigated and discussed. In addition, dimeric and binuclear Ni(II) and Fe(III) complexes of the diimines have been synthesized and characterized by physical and spectroscopic techniques. Also, in vitro antimicrobial activities of the diimines and the complexes have been evaluated against three bacteria: Micrococcus luteus (NRLL B-4375), Bacillus cereus (RSKK 863), Escherichia coli (ATCC 11230) and the fungus: Candida albicans (ATCC 10239). ª 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).