Efficient Functionalization of Carbon Nanotubes with Porphyrin Dendrons via Click Chemistry

The attempt to decorate carbon nanotubes with organic molecules as a powerful means to form new functional materials has attracted broad attention in the scientific community. Here, we report the functionalization of single-walled carbon nanotubes (SWNTs) with zinc porphyrins (ZnP) using very mild conditions to afford a series of SWNTs-ZnP (1 and 2) electron donor-acceptor conjugates. Owing to the presence of either one or two ZnP, introduced via click chemistry, different absorption cross sections were realized. Important in this context is that the covalent linkages between SWNT and ZnP were corroborated by monitoring the diagnostic signature of the nitrogen atoms as part of the formed triazole ring by X-ray photoelectron spectroscopy (XPS). The resulting SWNTs-ZnP 1 and 2 were fully characterized. This characterization was complemented by a full-fledged investigation of their electrochemical and photophysical properties. In particular, appreciably strong electronic coupling between the photo- and electroactive constituents (i.e., SWNT and ZnP) led to rapid excited-state deactivation of ZnP via charge transfer to the nanotubes. Here, the different absorption cross sections throughout the visible part of the solar spectrum turned out to be valuable in enhancing the overall light-harvesting features. Upon photoexcitation, for both SWNTs-ZnP 1 and 2, radical ion pair states (i.e., reduced SWNT and oxidized ZnP) are formed. The charge-separated states decay to regenerate the singlet ground state with lifetimes of 820 and 200 ps for 1 and 2, respectively.