title: Fluorene-Perylene Diimide Arrays onto Graphene Sheets for Photocatalysis.
abstract: A facile approach for introducing photoactive poly(fluorene-perylene diimide) arrays (PFPDI) onto graphene sheets was accomplished. Noncovalent PFPDI/graphene ensembles formed via π-π stacking interactions between the two components and covalent PFPDI-graphene hybrids realized upon a Stille polycondensation reaction between an iodobenzyl-functionalized graphene, a 9,9-dialkyl substituted fluorene diboronic acid, and a 1,7-dibromo-PDI derivative were prepared. The morphology of PFPDI/graphene and PFPDI-graphene was evaluated by high-resolution transmission electron microscopy (HR-TEM), revealing the presence of even monolayered graphene sheets. Moreover, their photophysical and redox properties as assessed by electronic absorption spectroscopy and steady-state as well as time-resolved photoluminescence assays and electrochemistry, respectively, disclosed charge-transfer characteristics owing to the high photoluminescence quenching of PFPDI in the presence of graphene and the fast component attributed to the decay of the emission intensity of the singlet excited state of PFPDI in both PFPDI/graphene and PFPDI-graphene. Next, testing their ability to operate in energy conversion schemes, the PFPDI-graphene was successfully employed as catalyst for the reduction of 4-nitrophenol to 4-aminophenol. Notably, the kinetics for the reduction were enhanced by visible light photoirradiation as compared to dark conditions as well as the presence of PFPDI-graphene, contrasting the case where only PFPDI, in the absence of graphene, was employed. Finally, recycling of the catalyst PFPDI-graphene was achieved and reutilization in successive reduction reactions of 4-nitrophenol was found to proceed with the same efficiency.
authors.affiliation: Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation , 48 Vassileos Constantinou Avenue, 11635 Athens, Greece.
authors.forename: Anastasios
authors.initials: A
authors.lastname: Stergiou
authors.affiliation: Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation , 48 Vassileos Constantinou Avenue, 11635 Athens, Greece.
authors.forename: Nikos
authors.initials: N
authors.lastname: Tagmatarchis
keywords: charge transfer; donor−acceptor; fluorene; graphene; perylene; photocatalysis