Electron-Donating Behavior of Few-Layer Graphene in Covalent Ensembles with Electron-Accepting Phthalocyanines

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.