Exfoliation of graphite was achieved using a zinc phthalocyanine oligomer that is also an electron donor. The resulting functionalized graphene material was investigated by Raman and electron spectroscopy and was trialed in a photoelectrochemical cell.

This Minireview sheds light onto the electronic communication between, on one hand, low dimensional nanocarbonssingle and multiwalled 1D carbon nanotubes and 2D grapheneand, on the other hand, a variety of electroactive species en-route to novel electron donor-acceptor conjugates and hybrids in relation to their covalent and non-covalent chemistry, respectively. A common denominator to any of the highlighted conjugates/hybrids is charge transport across different scales, that is, from individual molecular conjugates/hybrids to morphologically controlled devices.

"Green" graphene: For the first time, the covalent attachment of a light-harvesting and electron-donating phthalocyanine to the basal plane of few-layer graphene is reported. Physicochemical characterizations reveal an ultrafast charge separation from the photoexcited phthalocyanine to few-layer graphene followed by a slower charge recombination.

We describe herein the first example of highly exfoliated graphene covalently linked to electron accepting phthalocyanines. The functionalization of the nanocarbon surface with alkylsulfonyl phthalocyanines was attained by means of a "click" chemistry protocol. The new ensemble was fully characterized (thermogravimetric analysis, atomic force microscopy, transmission electron microscopy and Raman, as well as ground-state absorption) and was studied in terms of electron donor-acceptor interactions in the ground and in the excited state. In particular, a series of steady-state and time-resolved spectroscopy experiments demonstrated photoinduced electron transfer from the graphene to the electron-accepting phthalocyanines. This is the first example of an electron donor-acceptor nanoconjugate, that is, few-layer graphene/phthalocyanine, pinpointing the uncommon electron donating character of graphene.

Four novel nanographene/porphyrin hybrids were prepared, characterized, and probed in solar energy conversion schemes. Exfoliation of graphite by means of immobilizing four different porphyrins onto the basal plane of graphene is accompanied by distinct electronic interactions in both the ground and the excited states. In the ground state, a strong loss in oscillator strength goes hand-in-hand with a notable broadening of the porphyrin transitions and, as such, attests to the shift of electron density from the electron donating porphyrins to nanographene. In the excited state, a nearly quantitative quenching of the porphyrin fluorescence is indicative of full charge transfer. The latter is corroborated by femtosecond transient absorption measurements, which reveal the generation of the one-electron oxidized radical cation of the porphyrins with absorption maxima at 490 and 625 nm in the visible region and conduction band electrons in nanographene with features at 890 and 1025 nm in the near infrared region. We have demonstrated the applicability of the new nanographene/porphyrin hybrids in, for example, solar cells. In this regard, the presence of flakes is crucial in terms of influencing the injection processes, preventing aggregation, and reducing recombination losses, which are commonly encountered in porphyrin-based DSSCs.