Abstract
Photo-active pi-conjugated molecules (quaterthiophene and phthalocyanine) are either encapsulated into the hollow core of single-walled carbon nanotubes or non-covalently stacked at their outer surface in order to elaborate hybrid nano-systems with new physical properties, providing practical routes to fit different requirements for potential applications. In this study, we are interested in the relationship between the structure and the opto-electronic properties. The structural properties are investigated mainly by x-ray diffraction and/or Transmission Electron Microscopy and Raman spectroscopy. We evidence that the supramolecular organizations of confined quaterthiophenes depend on the nanocontainer size whereas phthalocyanine encapsulation leads the formation of a 1D-phase for which the angle between the molecule ring and the nanotube axis is close to 32°. Confined phthalocyanine molecules display Raman spectra hardly altered with respect to the bulk phase, suggesting a rather weak interaction with the tubes. In contrast, the vibrational properties of the molecules stacked at the outer surface of tubes display important modifications. We assume a significant curvature of the phthalocyanine induced by the interaction with the tube walls and a change of the central atom position within the molecular ring, in good agreement with our DFT calculations.