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

Corrole macrocycles have broad application prospects in optoelectronics and biomedicine, yet the combined effects of central trivalent metal ions and fluorinated electron-withdrawing substituents on their electronic structures remain insufficiently understood. In this work, four Au(iii)/Ag(iii)-coordinated corrole complexes (Au-C, Au-C-F, Ag-C, Ag-C-F) were systematically studied via 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.