Unraveling Meso-Substituent Steric Effects on the Mechanism of Hydrogen Evolution Reaction in Ni^II Porphyrin Hydrides Using DFT Method.

ABSTRACT: Substituents at the meso-site of metalloporphyrins profoundly influence the hydrogen evolution reaction (HER) mechanism. This study employs density functional theory (DFT) to computationally analyze Ni^II-porphyrin and its hydrides derived from tetrakis(pentafluorophenyl)porphyrin molecules, presenting stereoisomers in ortho- or para-positions. The results reveal that the spatial resistance effect of meso-substituted groups at the ortho- and para-positions induces significant changes in Ni-N bond lengths, angles, and reaction dynamics. For ortho-position substituents forming complex I, a favorable 88.88 ų spherical space was created, facilitating proton coordination and the formation of H₂ molecules; conversely,

SUBMITTER: Li X 

PROVIDER: S-EPMC10934329 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature