The synthetic route toward new unsymmetric compartmental "end-off" Schiff-base ligands in a straightforward two-step reaction of 2,6-diformyl-4-methylphenol and two different amine components is presented. To demonstrate the versatility of this method, we have synthesized two different single-Schiff-base proligands, Hbpahmb and Hphmb, utilizing (2-aminoethyl) bis(2-pyridylmethyl)amine and (2-aminomethyl) pyridine, respectively. Subsequent reaction with thiosemicarbazide as the second amine component leads to the novel unsymmetric double-Schiff-base ligands {1-[3-[2-[bis(pyridin-2-ylmethyl) amino] ethyliminomethyl]-2-hydroxy-5-methylphenyl] methylidene} hydrazine carbothioamide (H(2)bpamptsc) and {1-[3-(pyridin-2-ylmethyliminomethyl)-2-hydroxy-5-methylphenyl]methylide ne} hydrazine carbothioamide (H(2)pmptsc). Both ligands provide two distinctly different coordination pockets: a rigid tridentate N, O, S donor set of the hydrazide compartment versus a rather flexible pentadentate (H(2)bpamptsc) or tridentate (H(2)pmptsc) nitrogen-rich chelating side arm. The reaction of the ligand H(2)bpamptsc with zinc(II) acetate and copper(II) perchlorate yields the heterobinuclear Cu - Zn complex [CuZn(bpamptsc)(u(2), eta(1)- OAc)-(MeCN)](ClO4) (1).