Modulating the oxygen affinity of porphyrins with metals, ligands, and functional groups: A DFT study.

ABSTRACT: The interaction between different metals (M), axial ligands (L), and ring substituents (R) in porphyrins was investigated using density functional theory. Different combinations of iron and cobalt as metal centers; imidazole, chlorine, and an n-heterocyclic carbene (NHC) as axial ligands, and unsubstituted, octaethyl-, and tetraphenyl-porphyrins were explored in their low, intermediate, and high-spin states, alongside oxygen affinity. Remarkably, the n-heterocyclic carbene enhanced the affinity of cobalt porphyrins to oxygen, with binding energies on average 4.4 kcal mol^-1 higher than FeP with the same ligand, and 0.78 kcal mol^-1 higher than FeP with imidazole. The planarity of the iron tetraphenyl porphyrin with imidazole compared to its ruffled cobalt counterpart is

SUBMITTER: Ovalle S 

PROVIDER: S-EPMC11624296 | biostudies-literature | 2025 Jan

REPOSITORIES: biostudies-literature