title: Nanostructuration of phenylenevinylenediimide-bridged silsesquioxane: from electroluminescent molecular J-aggregates to photoresponsive polymeric H-aggregates.
abstract: A new approach to control molecular aggregation of pi-conjugated chromophores in the solid state has been investigated. Our strategy was to use a modifiable bulky fragment which should induce a J-aggregation and offer the possibility to reach an H-aggregation upon its chemical modification by lateral slip of pi-conjugated molecules. The chosen fragment for that purpose was the hydrolyzable triethoxysilane function (Si(OEt)3). Our objective was to design and synthesize electroluminescent or solar cell hybrid organic-inorganic materials by the sol-gel process applied to a bifunctionalized silane. With this intention, the synthesis of the sol-gel processable phenylenevinylenediimide silsesquioxane 6 was accomplished and the study of spin-coated thin films of the pure silane precursor subjected or not to the sol-gel process has been carried out. Optical properties of 6 are consistent with the formation of J-aggregates in the solid state due to the steric hindrance introduced by the triethoxysilane units. Conversely, the spectroscopic behavior observed for the hybrid film 6F is attributed to an H-aggregation corresponding to a "card pack" orientation of the distyrylbenzeneimide chromophores in the compressed silicate network. Morevover, 6 and 6F also exhibited different electronic behaviors: light-emitting diodes exhibited high brightness with the native precursor 6 and almost no light output with the sol-gel processed silsesquioxane 6F. Photovoltaic cells showed the opposite behavior with low photocurrent generation in the precursor case and higher photocurrents with the sol-gel processed layers. These results provide a deeper understanding of the present self-assembly process that is strongly governed by the molecular packing of the oligosiloxane precursor.
authors.affiliation: Hétérochimie Moléculaire et Macromoléculaire UMR CNRS 5076, Ecole Nationale Supérieure de Chimie de Montpellier, 8 rue de l'Ecole Normale 34296 Montpellier Cedex 05, France.
authors.forename: Olivier J
authors.initials: OJ
authors.lastname: Dautel
authors.forename: Guillaume
authors.initials: G
authors.lastname: Wantz
authors.forename: Robert
authors.initials: R
authors.lastname: Almairac
authors.forename: David
authors.initials: D
authors.lastname: Flot
authors.forename: Lionel
authors.initials: L
authors.lastname: Hirsch
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Lere-Porte
authors.forename: Jean-Paul
authors.initials: JP
authors.lastname: Parneix
authors.forename: Françoise
authors.initials: F
authors.lastname: Serein-Spirau
authors.forename: Laurence
authors.initials: L
authors.lastname: Vignau
authors.forename: Joël J E
authors.initials: JJ
authors.lastname: Moreau