<p>Metallo-covalent organic frameworks (M-COFs) integrate organometallic and polymer principles, with salen-type ligands offering a robust means to stabilize transition metal (TM) centers. Dual metallosalen based ligand systems (TM₂C₂₂H₁₈N₄O₂) have been investigated using density functional theory (DFT) to elucidate how TM choice influences framework properties. The findings revealed that Sc, Ti, Y, and Zr atoms in these complexes exhibit pronounced out-of-plane distortions relative to the C₂₂H₁₈N₄O₂ ligand plane. Regarding thermodynamic stability, the Ti₂C₂₂H₁₈N₄O₂ and ZrC₂₂H₁₈N₄O₂ complexes show superior performance compared to neighboring complexes. However, the complexes containing Ti₂, Cr₂, Cu₂, Zr₂, Mo₂, and Cd₂ display less chemical stability relative to adjacent systems. Additionally, Mulliken charge analysis shows that Sc₂C₂₂H₁₈N₄O₂ and Y₂C₂₂H₁₈N₄O₂ carry significantly higher charges than the remainder of the series, suggesting enhanced electron modulation capabilities. These insights guide the rational design of salen-based M-COFs for high-performance electrocatalysis.</p>