Herritsch, Jan and Luy, Jan-Niclas and Rohlf, Sebastian and Gruber, Manuel and Klein, Benedikt P. and Kallaene, Matthias and Schweyen, Peter and Broering, Martin and Rossnagel, Kai and Tonner, Ralf and Gottfried, J. Michael (2020) Influence of Ring Contraction on the Electronic Structure of Nickel Tetrapyrrole Complexes: Corrole vs Porphyrin. ECS JOURNAL OF SOLID STATE SCIENCE AND TECHNOLOGY, 9 (6): 061005. ISSN 2162-8769, 2162-8777
Full text not available from this repository. (Request a copy)Abstract
The influence of the contracted corrole macrocycle, in comparison to the larger porphyrin macrocycle, on the electronic structure of nickel was studied with X-ray and ultraviolet photoelectron spectroscopy (XPS, UPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Synthesis and in situ characterization of the Ni complexes of octaethylporphyrin (NiOEP) and hexaethyldimethylcorrole (NiHEDMC) were performed in ultra-high vacuum. XPS and NEXAFS spectra reveal a +2 oxidation state and a low-spin d(8)electron configuration of Ni in both complexes, despite the formal trianionic nature of the corrole ligand. UPS, in combination with density functional theory (DFT) calculations, support the electronic structure of a Ni(II) corrole with a pi-radical character of the ligand. The NEXAFS spectra also reveal differences in the valence electronic structure, which are attributed to the size mismatch between the small Ni(II) center and the larger central cavity of NiOEP. Analysis of the gas-phase structures shows that the Ni-N bonds in NiOEP are 4%-6% longer than those in NiHEDMC, even when NiOEP adopts a ruffled conformation. The individual interactions that constitute the Ni-ligand bond are altogether stronger in the corrole complex, according to bonding analysis within the energy decomposition analysis and the natural orbitals for chemical valence theory (EDA-NOCV).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | X-RAY PHOTOELECTRON; MOLECULAR-STRUCTURE; NI(II) PORPHYRINS; METAL-COMPLEXES; BASIS-SETS; SPECTRA; SURFACE; CHEMISTRY; TETRAPHENYLPORPHYRIN; OCTAETHYLPORPHYRIN; XPS; Ultraviolet photoelectron spectroscopy; Physical properties of electronic materials; Chemical properties of electronic materials; Thin film growth; CVD; Physical vapor deposition |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 18 Mar 2021 09:23 |
| Last Modified: | 18 Mar 2021 09:23 |
| URI: | https://pred.uni-regensburg.de/id/eprint/44225 |
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