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Inverse Hypercorroles
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DOI：10.1021/acs.inorgchem.4c00344.png)
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Abstract
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Ground-state and time-dependent density functional theory (TDDFT) calculations with the long-range-corrected, Coulomb-attenuating CAMY-B3LYP exchange-correlation functional and large, all-electron STO-TZ2P basis sets have been used to examine the potential inverse hypercorrole character of meso-p-nitrophenyl-appended dicyanidocobalt(III) corrole dianions. The effect is most dramatic for 5,15-bis(p-nitrophenyl) derivatives, where it manifests itself in intense NIR absorptions. The 10-aryl groups in these complexes play a modulatory role, as evinced by experimental UV-visible spectroscopic and electrochemical data for a series of 5,15-bis(p-nitrophenyl) dicyanidocobalt(III) corroles. TDDFT (CAMY-B3LYP) calculations ascribe these features clearly to a transition from the corrole's a(2u)-like HOMO (retaining the D-4h irrep used for metalloporphyrins) to a nitrophenyl-based LUMO. The outward nature of this transition contrasts with the usual phenyl-to-macrocycle direction of charge transfer transitions in many hyperporphyrins and hypercorroles; thus, the complexes studied are aptly described as inverse hypercorroles.
Keywords:
FLUORESCENCE SIGNALING SYSTEMS
ELECTRONIC-STRUCTURE
SCREENING MODEL
CORROLES
SPECTRA
COPPER
SPECTROSCOPY
ABSORPTION
SOLVATION
SOLVENTS
Journal
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4.7
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4.9W
Citations:
10.5W
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