Localization/Delocalization of Charges in Bay-Linked Perylene Bisimides
| Autor: | Harald Ceymann, Chengyi Xiao, Christoph Lambert, Simone Di Motta, Wei Jiang, Fabrizia Negri, Linxiao Hao, Zhaohui Wang |
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| Přispěvatelé: | W. Jiang, C. Xiao, L. Hao, Z. Wang, H. Ceymann, C. Lambert, S. Di Motta, F. Negri |
| Rok vydání: | 2012 |
| Předmět: |
Exciton
Organic Chemistry CHARGE LOCALIZATION General Chemistry Photochemistry Electrochemistry Catalysis Fluorescence spectroscopy Ullmann reaction chemistry.chemical_compound Delocalized electron chemistry SPECTROELECTROCHEMISTRY N-TYPE SEMICONDUCTORS QUANTUM CHEMICAL CALCULATION Absorption (chemistry) Wave function PERYLENE BIS IMIDE Perylene |
| Zdroj: | Chemistry - A European Journal. 18:6764-6775 |
| ISSN: | 0947-6539 |
| DOI: | 10.1002/chem.201103954 |
| Popis: | The copper-mediated Ullmann coupling of 1,7-dibromoperylene bisimides afforded structurally perfect singly-linked perylene bisimide (PBI) arrays, whilst the homo-coupling of 1,12-dibromoperylene bisimides gave doubly-linked and triply-linked diperylene bisimides. The interactions of three bay-linked diperylene bisimides that differed in their linkage (singly, doubly, and triply) were investigated in their neutral and reduced forms (mono-anion to tetra-anion). UV/Vis absorption and fluorescence spectroscopy revealed different degrees of interaction, which was explained by exciton coupling and conjugation effects. The electrochemical properties and spectroelectrochemistry also showed quite-different degrees of PBI interactions in the reduced mixed-valence species, which was apparent by the observation of CT bands. The interpretation of the experimental findings was supported by spin-restricted and -unrestricted DFT and time-dependent TD-DFT calculations with the long-range-corrected CAM-B3LYP functional. Accordingly, the degree of interaction in both the neutral and reduced forms of the bay-linked PBIs was qualitatively in the order doubly linked |
| Databáze: | OpenAIRE |
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