“A new potentially hexadentate redox-active schiff base ligand, H2L = 2-((Z)-(2-(2-(2-((Z)-3,5-di‑tert‑butyl‑2-hydroxybenzylideneamino)phenylthio)ethylthio)phenylimino)methyl)-4,6-di‑tert-butylphenol, reacts with NiII(O2CCH3)2·4H2O and PdCl2 in CH3OH in the presence of air and Et3N affording isolation of yellow and red crystalline solids of composition [Ni(L)] (1) and [Pd2(L)Cl2].2CH2Cl2 (2), respectively. When examined by cyclic voltammetry (CV), 1 exhibits three quasireversible responses at E1/2 = 0.60 V (peak-to peak separation, ΔEp = 80 mV), 0.96 V (ΔEp = 80 mV) and 1.16 V (ΔEp = 160 mV) vs SCE (saturated calomel electrode); while 2 exhibits one quasireversible response at E1/2 = 1.185 V (peak-to peak separation, ΔEp = 130 mV). One electron oxidized species showed EPR spectrum correspond to ferromagnetically coupled system, S = 3/2 (S = 1 for NiII and S = ½ for phenoxyl radical). Structural analysis revealed that 1 is discrete mononuclear and 2 is discrete dinuclear coordination complex. In complex 1, each NiII is in distorted octahedral NiN2O2S2 environment where coordination is satisfied by two nitrogen atoms, two oxygen atoms and two sulfur atoms of the ligand. In complex 2, each Pd is in distorted square planner PdNOSCl environment where coordination is satisfied by one each nitrogen, oxygen and sulfur atoms of the ligand, and a chloride ion. DFT calculations at B3LYP-level of theory adequately describe the electronic structures of 1 and 2, containing a spin-unpaired d8 NiII ion and spin-paired d8 PdII ion. Time-dependent-DFT calculations on 1 and 2 shed light on the origin of UV−vis−NIR spectral absorptions.