Inverse Hypercorroles DOI Creative Commons
W. Ryan Osterloh, Nicolas Desbois, Jeanet Conradie

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(19), P. 8739 - 8749

Published: May 2, 2024

Ground-state and time-dependent density functional theory (TDDFT) calculations with the long-range-corrected, Coulomb-attenuating CAMY-B3LYP exchange-correlation large, all-electron STO-TZ2P basis sets have been used to examine 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. 10-aryl groups these complexes play a modulatory role, as evinced by experimental UV–visible spectroscopic electrochemical data series corroles. TDDFT (CAMY-B3LYP) ascribe features clearly transition from corrole's a2u-like HOMO (retaining D4h irrep metalloporphyrins) nitrophenyl-based LUMO. outward nature this contrasts usual phenyl-to-macrocycle direction charge transfer transitions many hyperporphyrins hypercorroles; thus, studied are aptly described inverse hypercorroles.

Language: Английский

Understanding Anionic Hyperporphyrins: TDDFT Calculations on Peripherally Deprotonated meso-Tetrakis(4-hydroxyphenyl)porphyrin DOI Creative Commons
Jeanet Conradie, Carl C. Wamser, Abhik Ghosh

et al.

The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

Presented herein is a DFT/TDDFT study of meso-tetrakis(4-hydroxyphenyl)porphyrin (H2[THPP]) and its O-deprotonated tetraanionic form; the latter was modeled as both free tetraanion with various counterions. Based on our calculations, experimentally observed hyperporphyrin spectra are attributed to an admixture phenol/phenoxide character into a2u-type HOMO tetraphenylporphyrin. The results in elevation orbital energy relation other frontier orbitals, which accounts for spectral redshifts. calculations underscore differences performance different exchange-correlation functionals. Thus, while popular hybrid functional B3LYP greatly exaggerates redshift far-red band H2[THPP], range-separated CAMY-B3LYP predicts more moderate redshift. latter, however, fails reproduce absorptions 550-600 nm range, potentially underscoring still imperfect modeling anionic hyperporphyrins.

Language: Английский

Citations

0
Inverse Hypercorroles DOI Creative Commons
W. Ryan Osterloh, Nicolas Desbois, Jeanet Conradie

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(19), P. 8739 - 8749

Published: May 2, 2024

Ground-state and time-dependent density functional theory (TDDFT) calculations with the long-range-corrected, Coulomb-attenuating CAMY-B3LYP exchange-correlation large, all-electron STO-TZ2P basis sets have been used to examine 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. 10-aryl groups these complexes play a modulatory role, as evinced by experimental UV–visible spectroscopic electrochemical data series corroles. TDDFT (CAMY-B3LYP) ascribe features clearly transition from corrole's a2u-like HOMO (retaining D4h irrep metalloporphyrins) nitrophenyl-based LUMO. outward nature this contrasts usual phenyl-to-macrocycle direction charge transfer transitions many hyperporphyrins hypercorroles; thus, studied are aptly described inverse hypercorroles.

Language: Английский

Citations

2