Resonance Raman Spectroscopy and Quantum-Chemical Calculations of Push−Pull Molecules: 4-Hydroxy-4‘-nitroazobenzene and Its Anion
| Autor: | Rômulo A. Ando, Fernando Fernández-Lázaro, and Antonio C. Borin, Paulo Sérgio da Silva Santos, Gianluca Camillo Azzellini, José L. Rodríguez-Redondo, Ángela Sastre-Santos |
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| Rok vydání: | 2007 |
| Předmět: |
Anions
Models Molecular Chemistry Methanol Resonance Raman spectroscopy Analytical chemistry Resonance Chromophore Spectrum Analysis Raman Photochemistry Acceptor Molecular electronic transition symbols.namesake Models Chemical Excited state Benzene Derivatives symbols Quantum Theory Molecule Physical and Theoretical Chemistry Raman spectroscopy Azo Compounds |
| Zdroj: | The Journal of Physical Chemistry A. 111:13452-13456 |
| ISSN: | 1520-5215 1089-5639 |
| Popis: | The deprotonation of the push-pull molecule 4-hydroxy-4'-nitroazobenzene leads to a substantial variation in the charge distribution over the donor and acceptor moieties in the D-pi-azo-pi-A system. The extra charge stabilizes the excited state, leading to a drastic red shift of ca. 100 nm in the lambda max of the electronic transition and consequently causes significant changes in the resonance Raman enhancement profiles. In the neutral species the chromophore involves several modes, as nu(CN), nu(NN), and nu s(NO2), while in the anion the selective enhancement of the nu s(NO2) and nu(CO-) modes indicates a greater geometric variation of the NO2 and CO- moieties in the resonant excited electronic state. The interpretation of the electronic transitions and the vibrational assignment are supported by quantum-mechanical calculations, allowing a consistent analysis of the enhancement patterns observed in the resonance Raman spectra. |
| Databáze: | OpenAIRE |
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