Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 19, Issue 23, Pages 7532-7546Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201203869
Keywords
density functional calculations; heterocycles; nanostructures; noncovalent interactions; oligomers
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Funding
- Ministere de la Recherche
- Centre National de la Recherche Scientifique (CNRS)
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-Conjugated thienylenephenylene oligomers with fluorinated and dialkoxylated phenylene fragments have been designed and prepared to understand the interactions in fragment orbitals, the influence of the substituents (F, OMe) on the HOMOLUMO gap, and the role of intramolecular non-covalent cumulative interactions in the construction of -conjugated nanostructures. Their strong conjugation was also evidenced in the gas phase by UV photoelectron spectroscopy and theoretical calculations. These results can be explained by the crucial role of the relative energetic positions of the orbitals of the dimethoxyphenylene, which was used to model the dialkoxyphenylene entity, in determining the /* orbital levels of the fluorinated phenylene entity. Dialkoxyphenylenes raise the HOMO orbitals, whereas fluorinated phenylenes lower the LUMO orbitals in the oligomers. In addition, the presence of SF and HF interactions in the fluorinated phenylenethienylene compounds add to the SO interactions in the mixed targets and contribute to the full conjugation in the oligomer, inducing weak inter-ring angles between the involved aromatic cycles. These results, which showed extended conjugation of the system, were corroborated by a narrow HOMOLUMO gap (according to DFT calculations) and by a relatively strong maximum wavelength (as obtained by TD-DFT calculations and experimental UV/Vis measurements). The crystallographic data of two mixed thienylene(fluorinated and dialkoxylated phenylene) five-ring oligomers agree with the above results and show the formation of quasi-planar conformations with non-covalent SO, HF, and SF interactions. These studies in the solid and gas phases show the relevance of associating dialkoxyphenylene and fluorinated phenylene fragments with thiophene to lead to oligomers with improved electronic delocalization for electronic or optoelectronic devices.
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