Moll, Johannes and Naumann, Robert and Sorge, Lukas and Foerster, Christoph and Gessner, Niklas and Burkhardt, Lukas and Ugur, Naz and Nuernberger, Patrick and Seidel, Wolfram and Ramanan, Charusheela and Bauer, Matthias and Heinze, Katja (2022) Pseudo-Octahedral Iron(II) Complexes with Near-Degenerate Charge Transfer and Ligand Field States at the Franck-Condon Geometry. CHEMISTRY-A EUROPEAN JOURNAL, 28 (57): e202201858. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
Increasing the metal-to-ligand charge transfer (MLCT) excited state lifetime of polypyridine iron(II) complexes can be achieved by lowering the ligand's pi* orbital energy and by increasing the ligand field splitting. In the homo- and heteroleptic complexes [Fe(cpmp)(2)](2+) (1(2+)) and [Fe(cpmp)(ddpd)](2+) (2(2+)) with the tridentate ligands 6,2''-carboxypyridyl-2,2'-methylamine-pyridyl-pyridine (cpmp) and N,N'-dimethyl-N,N'-di-pyridin-2-ylpyridine-2,6-diamine (ddpd) two or one dipyridyl ketone moieties provide low energy pi* acceptor orbitals. A good metal-ligand orbital overlap to increase the ligand field splitting is achieved by optimizing the octahedricity through CO and NMe units between the coordinating pyridines which enable the formation of six-membered chelate rings. The push-pull ligand cpmp provides intra-ligand and ligand-to-ligand charge transfer (ILCT, LL'CT) excited states in addition to MLCT excited states. Ground and excited state properties of 1(2+) and 2(2+) were accessed by X-ray diffraction analyses, resonance Raman spectroscopy, (spectro)electrochemistry, EPR spectroscopy, X-ray emission spectroscopy, static and time-resolved IR and UV/Vis/NIR absorption spectroscopy as well as quantum chemical calculations.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | TRANSITION-METAL-COMPLEXES; X-RAY-ABSORPTION; GRAPHICAL USER-INTERFACE; BASIS-SETS; PHOTOPHYSICAL PROPERTIES; COORDINATION-COMPOUNDS; CARBENE COMPLEX; LIGHT; PHOTOCHEMISTRY; EFFICIENCY; iron; photophysics; polypyridine ligands; time-resolved spectroscopy; tridentate ligands |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Physical Chemistry I > Prof. Dr. Patrick Nürnberger |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 20 Feb 2024 07:31 |
| Last Modified: | 20 Feb 2024 07:31 |
| URI: | https://pred.uni-regensburg.de/id/eprint/58184 |
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