29938-08-7Relevant academic research and scientific papers
How to build fully π-conjugated architectures with thienylene and phenylene fragments
Lois, Sandrine,Flores, Jean-Charles,Lere-Porte, Jean-Pierre,Serein-Spirau, Francoise,Moreau, Joel J. E.,Miqueu, Karinne,Sotiropoulos, Jean-Marc,Baylere, Patrick,Tillard, Monique,Belin, Claude
, p. 4019 - 4031 (2008/02/13)
A series of small-sized model π-conjugated oligomers have been prepared from thienylene and phenylene or dimethyl-or dimethoxy-substituted phenylene units. Crystallographic data for the methoxylated compound show a quasi-planar conformation with a non-covalent S-O interaction. The resulting strong conjugation in the gas phase has also been highlighted by UV/photoelectron spectroscopy and theoretical calculations (DFT). Indeed, for these compounds there is a large energy gap ΔEπ arising from the interaction between the molecular orbitals of the isolated thienylene-phenylene species. This can be explained in terms of the energies of the two π orbitals of the dimethoxyphenylene unit, the shape of these molecular orbitals in a three-orbital interaction diagram and by the presence of the S...O interaction which reduces the inter-ring angle between the two aromatic cycles. The nature of the sulfur-oxygen interaction, discussed from a theoretical point of view, is mainly electrostatic, the orbital contribution from the only correctly directed orbitals nOσ and σ*S-C being slightly stabilising. These results show extensive conjugation of the π system corroborated by a small HOMO-LUMO gap. These studies, carried out in the solid state and in the gas phase, show how important it is to combine thienylene and dialkoxyphenylene fragments to obtain oligomers with a strong electronic delocalisation. Thus, these compounds are of interest in the fields of electronic and optoelectronic devices. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Synthesis of the bisbenzannelated spiroketal core of the γ-rubromycins. The use of a novel Nef-type reaction mediated by Pearlman's catalyst
Capecchi, Tanya,De Koning, Charles B.,Michael, Joseph P.
, p. 2681 - 2688 (2007/10/03)
The synthesis of the bisbenzannelated spiroketal core 6 of γ-rubromycin 1 from the substituted nitrostyrene 20 was achieved by using a novel Nef-type reaction mediated by Pearlman's catalyst. The precursor 28 was synthesised from readily prepared starting materials using Henry condensation chemistry. The product 6 was found to exist in two conformations in solution as shown by NMR spectroscopy.
