| Autor: |
Osterloh WR; ICMUB (UMR CNRS 6302), Université de Bourgogne, 9, Avenue A. Savary, BP 47870, 21078 Dijon Cedex, France.; Department of Chemistry, University of Houston, Houston, Texas 77204-5003, United States., Desbois N; ICMUB (UMR CNRS 6302), Université de Bourgogne, 9, Avenue A. Savary, BP 47870, 21078 Dijon Cedex, France., Conradie J; Department of Chemistry, UiT - The Arctic University of Norway, N-9037 Tromso̷, Norway.; Department of Chemistry, University of the Free State, 9300 Bloemfontein, Republic of South Africa., Gros CP; ICMUB (UMR CNRS 6302), Université de Bourgogne, 9, Avenue A. Savary, BP 47870, 21078 Dijon Cedex, France., Kadish KM; Department of Chemistry, University of Houston, Houston, Texas 77204-5003, United States., Ghosh A; Department of Chemistry, University of the Free State, 9300 Bloemfontein, Republic of South Africa. |
| Abstrakt: |
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. |
