Szeghalmi, Adriana V. and Erdmann, Marco and Engel, Volker and Schmitt, Michael and Amthor, Stephan and Kriegisch, Volker and Noell, Gilbert and Stahl, Rainer and Lambert, Christoph and Leusser, Dirk and Stalke, Dietmar and Zabel, Manfred and Popp, Juergen (2004) How delocalized is N,N,N',N'-tetraphenylphianylenediamine radical cation? An experimental and theoretical study on the electronic and molecular structure. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 126 (25). pp. 7834-7845. ISSN 0002-7863,
Full text not available from this repository. (Request a copy)Abstract
The electronic and molecular structure of N,N,N',N'-tetraphenylphenylenediamine radical cation 11 is in focus of this study. Resonance Raman experiments showed that at least eight vibrational modes are strongly coupled to the optical charge resonance band which is seen in the NIR. With the help of a DFT-based vibrational analysis, these eight modes were assigned to symmetric vibrations. The contribution of these symmetric modes to the total vibrational reorganization energy is dominant. These findings are in agreement with the conclusions from a simple two-state two-mode Marcus-Hush analysis which yields a tiny electron-transfer barrier. The excellent agreement of the X-ray crystal structure analysis and the DFT computed molecular structure of 11 on one hand as well as the solvent and solid-state IR spectra and the DFT-calculated IR active vibrations on the other hand prove 1(+) adopts a symmetrical delocalized Robin-Day class III structure both in the solid state and in solution.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | MIXED-VALENCE SYSTEMS; CHARGE-TRANSFER TRANSITIONS; DENSITY-FUNCTIONAL THEORY; RAMAN INTENSITY ANALYSIS; NEAR-INFRARED REGION; CREUTZ-TAUBE ION; RESONANCE RAMAN; REORGANIZATION ENERGIES; METAL-COMPLEXES; ELECTROABSORPTION SPECTROSCOPY; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Central Analytical Services |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 12 Jul 2021 10:24 |
| Last Modified: | 12 Jul 2021 10:24 |
| URI: | https://pred.uni-regensburg.de/id/eprint/37527 |
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