3,4-Dithiaphosphole and 3,3′,4,4′-tetrathia-1,1′- biphosphole π-conjugated systems: S makes the impact

Omrane Fadhel, Zoltán Benkö, Michael Gras, Valérie Deborde, Damien Joly, Christophe Lescop, L. Nyulászi, Muriel Hissler, Regis Réau

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)11340-11356
Number of pages17
JournalChemistry - A European Journal
Volume16
Issue number37
DOIs
Publication statusPublished - Oct 4 2010

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Atoms
Bearings (structural)
Alkadienes
Electropolymerization
Electronic properties
Polymers
Carbon
Stabilization
X ray diffraction
Oxidation
Acids
1,21-diamino-4,9,13,18-tetraazahenicosane
S(8)

Keywords

  • Conjugation
  • Density functional calculations
  • Electro-polymerization
  • Phospholes
  • Polymerization
  • Thiophenes

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

3,4-Dithiaphosphole and 3,3′,4,4′-tetrathia-1,1′- biphosphole π-conjugated systems : S makes the impact. / Fadhel, Omrane; Benkö, Zoltán; Gras, Michael; Deborde, Valérie; Joly, Damien; Lescop, Christophe; Nyulászi, L.; Hissler, Muriel; Réau, Regis.

In: Chemistry - A European Journal, Vol. 16, No. 37, 04.10.2010, p. 11340-11356.

Research output: Contribution to journalArticle

Fadhel, O, Benkö, Z, Gras, M, Deborde, V, Joly, D, Lescop, C, Nyulászi, L, Hissler, M & Réau, R 2010, '3,4-Dithiaphosphole and 3,3′,4,4′-tetrathia-1,1′- biphosphole π-conjugated systems: S makes the impact', Chemistry - A European Journal, vol. 16, no. 37, pp. 11340-11356. https://doi.org/10.1002/chem.201001463
Fadhel, Omrane ; Benkö, Zoltán ; Gras, Michael ; Deborde, Valérie ; Joly, Damien ; Lescop, Christophe ; Nyulászi, L. ; Hissler, Muriel ; Réau, Regis. / 3,4-Dithiaphosphole and 3,3′,4,4′-tetrathia-1,1′- biphosphole π-conjugated systems : S makes the impact. In: Chemistry - A European Journal. 2010 ; Vol. 16, No. 37. pp. 11340-11356.
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AU - Benkö, Zoltán

AU - Gras, Michael

AU - Deborde, Valérie

AU - Joly, Damien

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