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Fluorine substitution vs. central metal regulation: electronic properties and intrinsic reactivity of Au( iii )- and Ag( iii )-coordinated corroles from comprehensive DFT calculations

Year: 2026
Type: article
Abstract: density functional theory (DFT) calculations at the M06-2X/def2-TZVP/SMD level. Multi-index bonding analysis methods, atomic charge population, conceptual DFT reactivity descriptors, frontier molecular orbital (FMO), LOL-π delocalization, multicenter bond order, NICS-AICD aromaticity evaluation and IRI weak interaction visualization were jointly adopted to reveal the dual modulation effect of metal centers and fluorine substitution. Bond order results prove N-Au coordination bonds possess stronger orbital overlap than N-Ag bonds; fluorine's strong electronegativity raises the positive charge of central metal ions and slightly weakens metal-nitrogen bonding interaction. CDFT and FMO analyses demonstrate fluorination widens the HOMO-LUMO gap, elevates ionization potential and electrophilicity index, and reduces nucleophilicity, which increases chemical hardness and kinetic resistance toward chemical perturbation while enhancing electron-accepting capacity. Aromaticity characterizations including multicenter bond order, NICS and AICD confirm Au(iii) corroles exhibit stronger macrocyclic aromaticity than Ag(iii) analogues, and fluorine substitution disperses delocalized π-electrons and weakens overall aromaticity. IRI mapping confirms fluorine perturbs intramolecular van der Waals interactions. This work systematically elucidates the independent and synergistic regulatory mechanisms of metal species and fluorine substituents, providing quantitative baseline theoretical references for corrole-based photofunctional materials and biosensing-related research.
Source: RSC Advances
DOI: 10.1039/d6ra07081g
Institution: Heze University
Language: English
Open Access status: gold
Estimated APC paid: $1,042
OpenAlex ID: W7221576812
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Cites: 51
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Related to: 10