Pi-stacking functionalization through micelles swelling: Application to the synthesis of single wall carbon nanotube/porphyrin complexes for energy transfer

We report on a new, orginal and efficient method for pi-stacking functionalization of single wall carbon nanotubes. This method is applied to the synthesis of a high-yield light-harvesting system combining single wall carbon nanotubes and porphyrin molecules. We developed a micelle swelling technique that leads to controlled and stable complexes presenting an efficient energy transfer. We demonstrate the key role of the organic solvent in the functionalization mechanism. By swelling the micelles, the solvent helps the non water soluble porphyrins to reach the micelle core and allows a strong enhancement of the interaction between porphyrins and nanotubes. This technique opens new avenues for the functionalization of carbon nanostructures.

Excitation transfer and luminescence in porphyrin-carbon nanotube complexes

Functionalization of carbon nanotubes with hydrosoluble porphyrins (TPPS) is achieved by $pi$-stacking. The porphyrin/nanotube interaction is studied by means of optical absorption, photoluminescence and photoluminescence excitation spectroscopies. The main absorption line of the porphyrins adsorbed on nanotubes exhibits a 120 meV red shift, which we ascribe to a flattening of the molecule in order to optimize $pi-pi$ interactions. The porphyrin-nanotube complex shows a strong quenching of the TPPS emission while the photoluminescence intensity of the nanotubes is enhanced when the excitation laser is in resonance with the porphyrin absorption band. This reveals an efficient excitation transfer from the TPPS to the carbon nanotube.