Abstract
A novel family of nanocarbon‐based materials was designed, synthesized, and probed within the context of charge‐transfer cascades. We integrated electron‐donating ferrocenes with light‐harvesting/electron‐donating (metallo)porphyrins and electron‐accepting graphene nanoplates (GNP) into multicomponent conjugates. To control the rate of charge flow between the individual building blocks, we bridged them via oligo‐p‐phenyleneethynylenes of variable lengths by β‐linkages and the Prato–Maggini reaction. With steady‐state absorption, fluorescence, Raman, and XPS measurements we realized the basic physico‐chemical characterization of the photo‐ and redox‐active components and the multicomponent conjugates. Going beyond this, we performed transient absorption measurements and corroborated by single wavelength and target analyses that the selective (metallo)porphyrin photoexcitation triggers a cascade of charge transfer events, that is, charge separation, charge shift, and charge recombination, to enable the directed charge flow. The net result is a few nanosecond‐lived charge‐separated state featuring a GNP‐delocalized electron and a one‐electron oxidized ferrocenium.
Highlights
In 2004, graphene moved into the center of attention when Geim and co-workers isolated for the first time singlelayers of honeycomb networks based on sp2-hybridized carbon atoms by using adhesive tape.[1]
Considering the large-scale applications of few-layered graphene-based materials we have investigated for the first time the functionalization of a new carbon-based material: graphene nanoplates (GNP)
Using a short ultrasound treatment in isopropylic alcohol, the wormlike overall structures were removed from GNPs
Summary
In 2004, graphene moved into the center of attention when Geim and co-workers isolated for the first time singlelayers of honeycomb networks based on sp2-hybridized carbon atoms by using adhesive tape.[1]. Their utilization allows for a much better overall stability of the respective graphene dispersions It affords highly versatile functional materials with photo- and redox-active constituents. R. Pizzoferrato Department of Industrial Engineering, University of Rome Tor Vergata Via del Politecnico 1, 00133 Rome (Italy) [+] These authors contributed to this work. The design of graphene-based functional materials for charge-transfer applications requires suitable methods and choices of redox- and photo-active constituents. In terms of molecular building blocks, we decided to explore (metallo)porphyrins and ferrocenes conjugates owing to their different strength of electron-donation This approach is similar to that we explored in fullerene-based electron donor-acceptor conjugates, which exhibit long-lived charge-separated states as the product of a cascade of several charge-transfer events.[32] In particular, we focused on the synthesis of b-modified porphyrins, which feature electron-accepting. A unique feature of our nanocarbon-based materials is the b-linkage at the (metallo)porphyrins to modulate the electron donor-acceptor interactions
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