Construction d’oligomères conjugués par ingénierie moléculaire
Les séquences thiénylènes dialkoxybenzenes très conjuguées grâce à l’interaction
non covalente S…O
In these compounds there is a large energy gap ΔEπ arising from
the interaction between the molecular orbitals of the isolated
thienylene-dialkoxyphenylene 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 with a small HOMO–
LUMO gap and how important it is to combine thienylene and
dialkoxyphenylene fragments to obtain oligomers with a strong
electronic delocalisation.
How to build fully -conjugated architectures with thienylene and phenylene fragments.
S. LOIS ; J.-C. FLORES ; J.-P. LERE-PORTE ; F. SEREIN-SPIRAU; J. J. E. MOREAU ; K.
MIQUEU ; J.-M. SOTIROPOULOS ; P. BAYLERE ; M. TILLARD ; C. BELIN. Eur. J. Org. Chem.,
2007, 4019-4031.
Caractérisation de l’interaction S…O par spectroscopie IR dans le bas domaine
Non-covalent S⋯O interactions are studied in
oligo(thienylene-2,5-dialkoxyphenylene). Farinfrared measurements coupled to density
functional theory are used. The most sensitive
modes to the S⋯O interactions are located
around 300 cm−1. They are assigned to in-plane
shear of thiophene rings coupled to the methoxy
groups.
Far-infrared spectroscopy investigation of sulfur-oxygen interactions in pi-conjugated oligomers.
P. HERMET ; J.-L. BANTIGNIES ; J.-P. LERE-PORTE ; F . SEREIN-SPIRAU, Chem. Phys. Lett.,
2012, 535, 116-119.
Compréhension du rôle des fragments pour élaborer des oligomères pi-conjugués
Thienylene phenylene oligomers with
fluorinated and dialkoxylated phenylene
fragments have been designed and
prepared. UV photoelectron spectroscopy
and DFT calculations highlight how the
resulting strong conjugation depends on
the energetics of the π orbitals of the
molecular fragments, which are related to
the nature of the substituents (F, OMe) on
the phenylene groups
Comprehensive analysis of fragments orbitals interactions to build highly -conjugated
thienylene-substituted phenylene oligomers
J.-C. FLORES, M.-A. LACOUR ; X. SALLENAVE ; F. SEREIN-SPIRAU ; J.-P. LERE-PORTE ; J.
J. E. MOREAU ; K. MIQUEU ; J.-M. SOTIROPOULOS ; D. FLOT. Chem. Eur. J. 2013, 19, 75527546.