Dihedral-Angle-Controlled Crossover from Static Hole Delocalization to Dynamic Hopping in Biaryl Cation Radicals
| Autor: | Rajendra Rathore, Ruchi Shukla, Tushar S. Navale, Maxim V. Ivanov, Marat R. Talipov, Mohammad Mosharraf Hossain |
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| Rok vydání: | 2016 |
| Předmět: |
Coupling
One half Magnetic Resonance Spectroscopy Free Radicals Molecular Structure Series (mathematics) 010405 organic chemistry Chemistry Radical Aryl Crossover General Chemistry Reference Standards Dihedral angle 010402 general chemistry 01 natural sciences Molecular physics Catalysis 0104 chemical sciences chemistry.chemical_compound Delocalized electron Cations Quantum Theory Organic chemistry |
| Zdroj: | Angewandte Chemie International Edition. 56:266-269 |
| ISSN: | 1433-7851 |
| DOI: | 10.1002/anie.201609695 |
| Popis: | In cases of coherent charge-transfer mechanism in biaryl compounds the rates follow a squared cosine trend with varying dihedral angle. Herein we demonstrate using a series of biaryl cation radicals with varying dihedral angles that the hole stabilization shows two different regimes where the mechanism of the hole stabilization switches over from (static) delocalization over both aryl rings to (dynamic) hopping. The experimental data and DFT calculations of biaryls with different dihedral angles unequivocally support that a crossover from delocalization to hopping occurs at a unique dihedral angle where the electronic coupling (Hab) is one half of reorganization (λ), that is, Hab=λ/2. The implication of this finding in non-coherent charge-transfer rates is being investigated. |
| Databáze: | OpenAIRE |
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