biostudies-literatureLi XProvincial Key Research and Development Program of ShaanxiKey Project of Baoji University of Arts and Sciencesthe Special project of philosophy and Social science of BaojiChina Postdoctoral Science FoundationFeng AL is supported by The Thousand Talents Plan for Yong Professionals of Shannxi Province and High-level Leading Talents of Scientific and Technological Innovation of BaojiFeng ailingthe Natural Science Basic Research Plan in Shanxi Province of China986https://www.ebi.ac.uk/biostudies/studies/S-EPMC10934329biostudies-literatureUnknown29(5)Substituents at the <i>meso-</i>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 <i>ortho-</i> or <i>para</i>-positions. The results reveal that the spatial resistance effect of <i>meso</i>-substituted groups at the <i>ortho-</i> and <i>para-</i>positions induces significant changes in Ni-N bond lengths, angles, and reaction dynamics. For <i>ortho-</i>position substituents forming complex <b>I</b>, a favorable 88.88 ų spherical space was created, facilitating proton coordination and the formation of H₂ molecules; conversely, Molecules (Basel, Switzerland)Unraveling Meso-Substituent Steric Effects on the Mechanism of Hydrogen Evolution Reaction in Ni^II Porphyrin Hydrides Using DFT Method.PMC10934329noBJSKZX-202263209040127, ZK20180512016M6018782019GY-1972015JM521551801001Li XLiu PZu YFeng AfalseUnraveling Meso-Substituent Steric Effects on the Mechanism of Hydrogen Evolution Reaction in Ni^II Porphyrin Hydrides Using DFT Method.Substituents at the <i>meso-</i>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 <i>ortho-</i> or <i>para</i>-positions. The results reveal that the spatial resistance effect of <i>meso</i>-substituted groups at the <i>ortho-</i> and <i>para-</i>positions induces significant changes in Ni-N bond lengths, angles, and reaction dynamics. For <i>ortho-</i>position substituents forming complex <b>I</b>, a favorable 88.88 ų spherical space was created, facilitating proton coordination and the formation of H₂ molecules; conversely, 2024-01-01T00:00:00Z2024 Feb2025-04-04T12:58:36.697Z2025-04-04T12:58:36.697ZS-EPMC109343293847449810.3390/molecules29050986