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- Christensen, M. A., et al.
(författare)
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Mixed valence radical cations and intermolecular complexes derived from indenofluorene-extended tetrathiafulvalenes
- 2014
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Ingår i: Journal of Materials Chemistry C. - : Royal Society of Chemistry (RSC). - 2050-7534 .- 2050-7526. ; 2:48, s. 10428-10438
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Tidskriftsartikel (refereegranskat)abstract
- Engineering of mixed-valence (MV) radical cations and intermolecular complexes based on pi-extended tetrathiafulvalenes (TTFs) is central for the development of organic conductors. On another front, redox-controlled dimerization of radical cations has recently been recognized as an important tool in supramolecular chemistry. Here we show that pi-extended TTFs based on the indenofluorene core, prepared by Horner-Wadsworth-Emmons reactions, undergo reversible and stepwise one-electron oxidations and that the detectable, intermediate radical cation forms remarkably strong intermolecular MV ([neutral.cation]) and pi-dimer ([cation.cation]) complexes with near-infrared radical cation absorptions. The radical cation itself seems to be a so-called Class III MV species in the Robin-Day classification. The formation of MV dimers was corroborated by ESR spectroelectrochemical studies, revealing two slightly different ESR signals upon oxidation, one assigned to the MV dimer and the other to the cation monomer. Crystals of the radical cation with different anions (PF6- , BF4-, and TaF6-) were grown by electrocrystallization. Conductance studies revealed that the salts behave as semiconductors with the hexafluorotantalate salt exhibiting the highest conductance. Using a custom-built ESR spectrometer with sub-femtomole sensitivity, the magnetic properties of one crystal were investigated. While the spin-to-spin interaction between radical cations was negligible, a high cooperativity coupling to the microwave field was observed - as a result of an exceptionally narrow spin line width and high spin density. This could have great potential for applications in quantum computation where crystalline spin ensembles are exploited for their long coherence times.
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| 2. |
- Lousen, B., et al.
(författare)
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Compressing a Non-Planar Aromatic Heterocyclic [7]Helicene to a Planar Hetero[8]Circulene
- 2020
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 26:22, s. 4935-4940
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Tidskriftsartikel (refereegranskat)abstract
- This work describes a synthetic approach where a non-planar aromatic heterocyclic [7]helicene is compressed to yield a hetero[8]circulene containing an inner antiaromatic cyclooctatetraene (COT) core. This [8]circulene consists of four benzene rings and four heterocyclic rings, and it is the first heterocyclic [8]circulene containing three different heteroatoms. The synthetic pathway proceeds via a the flattened dehydro-hetero[7]helicene, which is partially a helicene and partially a circulene: it is non-planar and helically chiral as helicenes, and contains a COT motif like [8]circulenes. The antiaromaticity of the COT core is confirmed by nucleus independent chemical shift (NICS) calculations. The planarization from a helically π-conjugated [7]helicene to a fully planar heterocyclic [8]circulene significantly alters the spectroscopic properties of the molecules. Post-functionalization of the [7]helicenes and the [8]circulenes by oxygenation of the thiophene rings to the corresponding thiophene-sulfones allows an almost complete fluorescence emission coverage of the visible region of the optical spectrum (400–700 nm).
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