The present study reports the synthesis and characterization of a family of three new neutral Zn(II), Cu(II), Co(II) bimetallic (2-4) and one ionic Co(II) trimetallic (5) complexes of ferrocene-containing unsymmetrically-substituted N 2 O 2 tetradentate Schiff base ligands. They were all prepared via a three-component one-pot template reaction involving the 4hydroxyphenyl substituted ferrocenyl-containing half unit Fc-C(=O)CH=C(4-C 6 H 4 OH)NH-CH 2 CH 2 NH 2 (Fc = ferrocenyl = (η 5 -C 5 H 5 )Fe(η 5 -C 5 H 4 )), metal(II) acetate and 5nitrosalicylaldehyde (for 2-4) or the organometallic salicylaldehyde [Cp*Ru(η 6 -2-OH-C 6 H 4 CHO)]PF 6 (for 5) (Cp* = η 5 -C 5 Me 5 ). The four complexes were isolated as air and moisture insensitive solids in yields > 80 %. They were characterized using several analytical techniques such as CHN analyses, ESI mass, FT-IR, UV-vis and NMR spectroscopy, including single crystal X-ray diffraction analysis. The crystal structure of 3 reveals that the four-coordinate copper atom adopts a square planar geometry with two nitrogen and two oxygen atoms as donors occupying cis positions. An electrochemical study utilizing cyclic voltammetry showed for each compound a reversible redox process ascribed to the Fe(II)/Fe(III) couple of the appended donor ferrocene. The largest anodic potentials were measured for the two Co(II) species. The second-order NLO responses of the push-pull chromophores 2-5 have been determined by harmonic light scattering measurements in N,Ndimethylformamide solutions at 1.91 μm incident wavelength, and rather high, non-resonant quadratic hyperpolarisability β values ranging from 140-280 x 10 -30 esu were determined.