A novel series of pyrene containing thiophene monomers TPM1-5 were synthesized and fully characterized by FTIR, MS, 1 H-and 13 C-NMR spectroscopy; their thermal properties were determined by TGA and DSC. These monomers were chemically polymerized using FeCl 3 as oxidizing agent to give the corresponding oligomers TPO1-5) and they were electrochemically polymerized to obtain the corresponding polymer films deposited onto ITO. All oligomers exhibited good thermal stability, with T 10 values between 255 and 299˝C, and T g values varying from 36 to 39˝C. The monomers showed an absorption band at 345 nm due to the S 0 Ñ S 2 transition of the pyrene group, whereas the fluorescence spectra showed a broad emission band arising from the "monomer" emission at 375-420 nm. The obtained polymers exhibited two absorption bands at 244 and 354 nm, due to the polythiophene and the pyrene moieties, respectively. The fluorescence spectra of polymers showed a broad "monomer" emission at 380-420 nm followed by an intense excimer emission band at 570 nm, due to the presence of intramolecular pyrene-pyrene interactions in these compounds.

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Thin polythiophene films were prepared by electrodeposition, using two novel thiophene monomers containing a pyrene unit linked via a flexible spacer. The obtained polymers have a suitable architecture for the further preparation of polymer composites with graphene via π-π interactions. Physicochemical characterization of the precursor polymers demonstrated that the resulting films are made of homogeneous electroactive polythiophene with pendant pyrene units regularly located on the polymer surface. These compounds are highly emissive and easily form excimers as other high pyrene content polymers. The polymer emission can be drastically quenched by the interaction with graphene after dipping the film into an aqueous suspension of reduced graphite oxide. The presence of aggregated graphene onto pyrene rich content areas by non-covalent interactions has been confirmed by AFM analysis. This kind of polythiophene/pyrene thin films showed to be a good matrix for the elaboration of fluorescent polymer composites.