The following report details the synthesis and characterization of two types of organic ligands namely, (4-X-phenyl)-pyridin-2-ylmethylene-amine (ppaX) {X = H, Me, OMe, Et, F, Cl, Br and I} and the briding ligands: bispyridylmethylene-1,3-benzeneamine (1,3-bpmba), bispyridylmethylene-1,4-benzeneamine (1,4-bpmba), bispyridylmethylene-1,5-naphthaleneamine (1,5-bpmna) and bis(pyridyl)methylene-hydrazone (bpmhd). The reaction between ppaX ligand and desired metal β-diketonate complexes yield monomeric complexes, [M(β-diketonate)2(ppaX)] (M = Ni and Co; β-diketonate = dbm, tmhd and hfac). The electron transfer studies show that these complexes are redox active. The oxidation potential is found to be dependent on the type β-diketonate ligand but essentially independent of the substituent, X, on the ppaX ligand which has been confirmed by DFT calculation of [M(β-diketonate)2(ppaX)] complexes. Interestingly, the Co complexes exhibit the redox coupled spin-crossover behavior. Further investigation has been explored by isolation the redox paired of [M(β-diketonate)2(ppaX)] and [M(β-diketonate)2(N-N)] (β- diketonate = dbm and tmhd; N-N = phen, bipy and dmae). Sharp signals in 1H NMR indicate that cationic complexes are Co(III) d6. The reaction of bridging ligands and metal β-diketonate complexes yield dimermeric complexes, [(β-diketonate)2M(µ-L)M(β-diketonate)2] (M = Ni and Co; β-diketonate = dbm and tmhd; L = bispyridylmethylene-1,3-benzeneamine (1,3-bpmba), bispyridylmethylene- 1,4-benzeneamine (1,4-bpmba), bispyridylmethylene-1,5-naphthaleneamine (1,5-bpmna) and bis(pyridyl)methylene-hydrazone (bpmhd). The cyclic voltammetry studies show that all Ni and Co complexes are redox active. The shorter bridging ligand give more communication between two metals. Furthermore, in case of Co complexes still exhibit redox coupled spincrossover behavior.