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

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

et al.

Published: Jan. 29, 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 minor modulatory role. 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. studied, therefore, are aptly described as inverse

Language: Английский

Citations

2
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