Cations and Anions of Dibenzo[a,e]pentalene and Reduction of a Dibenzo[a,e]pentalenophane
| Autor: | Mathias Hermann, Tobias Böttcher, Marcel Schorpp, Birgit Esser, Ingo Krossing, Daniel Wassy, Sabine Richert |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Pentalene
oxidation reduction Conjugated system 010402 general chemistry Photochemistry Pentalenes 01 natural sciences Catalysis chemistry.chemical_compound Delocalized electron organic field-effect transistors Full Paper 010405 organic chemistry Organic Chemistry radical anion Aromaticity General Chemistry Full Papers antiaromaticity 0104 chemical sciences Dication Bond length chemistry Derivative (chemistry) Antiaromaticity |
| Zdroj: | Chemistry (Weinheim an Der Bergstrasse, Germany) |
| ISSN: | 1521-3765 0947-6539 |
| Popis: | Dibenzo[a,e]pentalene (DBP) is a non‐alternant conjugated hydrocarbon with antiaromatic character and ambipolar electrochemical behavior. Upon both reduction and oxidation, it becomes aromatic. We herein study the chemical oxidation and reduction of a planar DBP derivative and a bent DBP‐phane. The molecular structures of its planar dication, cation radical and anion radical in the solid state demonstrate the gained aromaticity through bond length equalization, which is supported by nucleus independent chemical shift‐calculations. EPR spectra on the cation radical confirm the spin delocalization over the DBP framework. A similar delocalization was not possible in the reduced bent DBP‐phane, which stabilized itself by proton abstraction from a solvent molecule upon reduction. This is the first report on structures of a DBP cation radical and dication in the solid state and of a reduced bent DBP derivative. Our study provides valuable insight into the charged species of DBP for its application as semiconductor. Aromatic character in a dibenzo[a,e]pentalene (DBP) was observed upon chemical oxidation to the cation radical and dication and reduction to the anion radical, as found from solid‐state structures. In a bent DBP‐phane aromaticity could not be reached upon reduction, and stabilization though proton abstraction occurred. |
| Databáze: | OpenAIRE |
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