Dye confinement into carbon nanotube significantly affects the electronic charge density distribution of the final hybrid system. Using the electron-phonon coupling sensitivity of the Raman G-band, we quantify experimentally how charge transfer from thiophene oligomers to single walled carbon nanotube is modulated by the diameter of the nano-container and its metallic or semiconducting character. This charge transfer is shown to restore the electron-phonon coupling into defected metallic nanotubes. For sub-nanometer diameter tube, an electron transfer optically activated is observed when the excitation energy matches the HOMO-LUMO transition of the confined oligothiophene. This electron doping accounts for an important enhancement of the photoluminescence intensity up to a factor of nearly six for optimal confinement configuration. This electron transfer shifts the Fermi level, acting on the photoluminescence efficiency. Therefore, thiophene oligomer encapsulation allows modulating the electronic structure and then the optical properties of the hybrid system.

As three‐dimensional folding is prerequisite to biopolymer activity, complex functions may also be achieved through foldamer science. Because of the diversity of sizes, shapes and folding available with synthetic monomers, foldamer frameworks enable a numerous opportunities for designing new generations of catalysts. We herein demonstrate that heterocyclic γ‐peptide scaffolds represent a versatile platform for enamine catalysis. One central feature was to determine how the catalytic activity and the transfer of chiral information might be under the control of the conformational behaviours of the oligomer.

Over the past two decades significant efforts have been directed towards the elucidation of synthesis/structure/function correlations to guide the development of synthetic strategies for controlling the composition, size and shape of nanomaterials. In this context, organic–inorganic nanohybrids incorporating bridged silsesquioxanes have been of particular interest, due to their versatility and the structural control that can be achieved through independent modulation of the properties of the organic bridge and inorganic moieties. Such strategies have also been applied to the production of thin films on a variety of substrates, driven by the continuous need to develop new and enhanced materials with nanostructures engineered over multiple length scales for applications in electronics, optics, sensing, ferromagnetic, shape-selective membranes, etc. In this talk, I will first present a fundamental study of the nanostructuring mechanisms of model hybrid silica. Our experimental investigation was performed using an in operando approach (vibrational spectroscopies under pressure, light diffusion, microscopy) coupled with DFT calculations. Parameters controlling the evolution of the system during sol−gel processing: supramolecular interactions, hydrolysis, polycondensation, and nucleation and growth of the hybrid solid in solution were investigated. The relation between structural properties and applications will be then highlighted1-4.

The high-pressure behavior of LuFe2O4 is characterized based on synchrotron X-ray diffraction and neutron diffraction, resistivity measurements, X-ray absorption spectroscopy and infrared spectroscopy studies. The results obtained enabled us to propose a P-T phase diagram. In this study, the low pressure charge-ordering melting could be detected by synchrotron XRD in the P-T space. In addition to the ambient pressure monoclinic C2/m and rhombohedral R(3) over bar m phases, the possible P (1) over bar triclinic phase, the monoclinic high pressure form Pm and metastable modulated monoclinic phases were observed; the latter modulated monoclinic phases were not observed in the present neutron diffraction data. Furthermore, the transition to the Pm phase which was already characterized by strong kinetics is found to be favored at high temperature (373 K). Based on X-ray absorption spectroscopy data the Pm phase, which could be recovered at atmospheric pressure, can be explained by a change in the Fe-local environment from a five-fold coordination to a distorted 5 + 1 one.

Encapsulating molecules inside nanotubes (called hybrid nanotubes in the following) is a common strategy to add new functionalities to the nanocontainer. The one-dimensional nature of single-walled carbon nanotubes (SWCNT) internal channels is exploited here to induce a molecular order and specific interactions which are dependent of the size of the nano container (figure). I present in this seminar the study of the relation between structural, vibrational and electronic properties of hybrid nanotubes encapsulating dyes. Dimethyl-quarterthiophene (4TCH3) encapsulated inside single-walled carbon nanotubes is studied by inelastic neutron scattering. The results reveal specific dynamics of the 4TCH3 modes characterized in particular by a large sensitivity in the low frequency domain of the methyl libration to the confinement. DFT based calculations consistently describe the observed phenomena and give insights on the structure of the hybrid nanotubes at low temperature where molecules preferentially interact with the nanotube wall. We evidence also by means of Raman spectroscopy and transmission electron microscopy that the supramolecular organizations of the confined oligothiophenes depend on the nanocontainer size. Charge transfer between the dyes and the nanocontainer is shown. A strong dependence on the infrared response of the hybrid nanotube due to confinement effect is finally investigated. The results are compared to experiments performed on nanotubes where dyes are π-stacked at the outer surface. Surprisingly, the confinement properties lead to an exaltation of the infrared absorption response in the carbon nanotubes from dye molecule interactions. Thanks to the comparison between the experimental investigations and DFT calculations, we elucidate the origin of the large enhancement of this infrared absorption.

Middle infrared response on a carbon nanotube is very weak because this homonuclear allotrope of carbon does not bear permanent dipoles. Nevertheless, a significant number of infrared phonons are predicted by the group theory. Encapsulating molecules inside nanotubes (called hybrid nanotubes in the following) is a common strategy to add new functionalities. The one-dimensional nature of single-walled carbon nanotubes (SWCNT) internal channels has been exploited here to induce a molecular order and specific interactions which are dependent of the size of the nano container.Here we report the discovery of a strong dependence on the infrared response of the hybrid nanotube due to confinement effect when dimethylquaterthiophenes are encapsulated inside SWCNTs. Results are compared to experiments performed on nanotubes where dyes are π-stacked at the outer surface. Surprisingly, the confinement properties lead to an exaltation of the infrared absorption response in the carbon nanotubes from dye molecule interactions. Thanks to the comparison between the experimental investigations and DFT calculations, we elucidate the origin of the large enhancement of this infrared absorption and demonstrate that interactions between conjugated oligomers and nanotubes can be probed.