title: Oligothiophene/graphene supramolecular ensembles managing light induced processes: preparation, characterization, and femtosecond transient absorption studies leading to charge-separation.
abstract: Advances in organic synthetic chemistry combined with the exceptional electronic properties of carbon allotropes, particularly graphene, is the basis used to design and fabricate novel electron donor-acceptor ensembles with desired properties for technological applications. Thiophene-based materials, which are mainly thiophene-containing polymers, are known for their notable electronic properties. In this frame moving from polymer to oligomer forms, new fundamental information would help for a better understanding of their electrochemical and photophysical properties. Furthermore, a successful combination of their electronic properties with those of graphene is a challenging goal. In this study, two oligothiophene compounds, which consist of three and nine thiophene-rings and are abbreviated 3T and 9T, respectively, were synthesized and noncovalently associated with liquid phase exfoliated few-layered graphene sheets (abbreviated eG), thus forming donor-acceptor 3T/eG and 9T/eG nanoensembes. Markedly, intra-ensemble electronic interactions between the two components in the ground and excited states were evaluated with the aid of UV-Vis and photoluminescence spectroscopy. Furthermore, redox assays revealed the one-electron oxidation of 3T accompanied by one-electron reduction due to eG in 3T/eG, whereas there were two reversible one-electron oxidations of 9T accompanied by one-electron reduction of eG9T/eG. The electrochemical band gap for the 3T/eG and 9T/eG ensembles were calculated and verified, in which the negative free-energy change for the charge-separated state of 3T/eG and 9T/eGvia the singlet excited state of 3T and 9T, respectively, were thermodynamically favorable. Finally, the results of transient pump-probe spectroscopy studies at the femtosecond time scale were supportive of charge transfer type interactions in the 3T/eG and 9T/eG ensembles. The estimated rates for intra-ensemble charge separation were found to be 9.52 × 10(9) s(-1) and 2.2 × 10(11) s(-1), respectively, for 3T/eG and 9T/eG in THF, which reveal moderate to ultrafast photoinduced events in the oligothiophene/graphene supramolecular ensembles.
authors.affiliation: Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, Athens 11635, Greece. tagmatar@eie.gr.
authors.forename: A
authors.initials: A
authors.lastname: Stergiou
authors.forename: H B
authors.initials: HB
authors.lastname: Gobeze
authors.forename: I D
authors.initials: ID
authors.lastname: Petsalakis
authors.forename: S
authors.initials: S
authors.lastname: Zhao
authors.forename: H
authors.initials: H
authors.lastname: Shinohara
authors.forename: F
authors.initials: F
authors.lastname: D'Souza
authors.forename: N
authors.initials: N
authors.lastname: Tagmatarchis