1256167-85-7Relevant academic research and scientific papers
3,4-Dithiaphosphole and 3,3′,4,4′-tetrathia-1,1′- biphosphole π-conjugated systems: S makes the impact
Fadhel, Omrane,Benkoe, Zoltan,Gras, Michael,Deborde, Valerie,Joly, Damien,Lescop, Christophe,Nyulaszi, Laszlo,Hissler, Muriel,Reau, Regis
, p. 11340 - 11356 (2010)
Conjugated systems based on phospholes and 1,1′-biphospholes bearing 3,4-ethylenedithia bridges have been prepared using the Fagan-Nugent route. The mechanism of this organo-metallic route leading to intermediate zirconacyclopentadienes has been investigated by using theoretical calculations. This study revealed that the oxidative coupling leading to zirconacyclo- pentadienes is favored over oxidative addition within the S-C ≡ C bond both thermodynamically and kinetically. The impact of the presence of the S atoms on the optical and electrochemical behavior of the phospholes and 1,1′-bi-phospholes has been systematically evaluated both experimentally and the oretically. A comparison with their all-carbon analogues is provided. Of particular interest, this comparative study revealed that the introduction of S atoms has an impact on the electronic properties of phosphole-based conjugated systems. A decrease of the HOMO-LUMO separation and a stabilization of the LUMO level were observed. These general trends are also observed with 1,1′-biphospholes exhibiting σ-π conjugation. The P atom of the 3,4-ethylenedithiaphospholes can be selectively oxidized by S 8 or O2. These P modifications result in a lowering of the HOMO-LUMO separation as well as an increase of the reduction and oxidation potentials. The S atoms of the 3,4-ethylenedithia bridge of the 2,5-phosphole have been oxidized using m-chloroperoxybenzoic acid. The resulting 3,4-ethylenesulfoxide oxophosphole was characterized by an X-ray diffraction study. Experimental and theoretical studies show that this novel chemical manipulation results in an increase of the HOMO-LUMO separation and an important decrease of the LUMO level. The electropolymerization of 2-thienyl-capped 3,4-ethylenedi-thiathioxophosphole and 1,1′-biphos-phole is reported. The impact of the S substituents on the polymer properties is discussed.
