Modeling of the infrared vibrational dynamics of oligothiophenes embedded in carbon nanotubes

Associations of organic and inorganic molecules involving non covalent and covalent interactions participate to a wide range of structures found in nature. Bridged silsesquioxanes (BS) can be designed with organic units selected to drive self-organization into a solid network. Therefore new hybrids functional materials with controlled morphologies can be synthesized. In particular urea groups, thanks to their ability to self-assemble though H bonds, have been incorporated in BS within the organic subunits (figure 1, UU). Depending on kinetics of the sol gel reaction, hybrid materials bridged by urea groups exhibiting a variety of textures and morphologies were synthetized. Considering the bridging group as a key element for the control of the assembly formed hybrids materials where thiourea groups have also been synthesized (Figure 1, UU or TT). As a matter of fact thiourea groups are also known to link them self via H bonds, but with geometry and strengths that can differ from urea links. Vibrational spectroscopy is used here to explore the self-organization mechanisms involved in the formation of urea bridged and thiourea bridged silsequioxanes. The influence of H-bonding strength and the self-organization properties of the urea and thiourea bridged organic substructures are explored through infra-red spectroscopy coupled with DFT calculations. Some particular vibrations such as amides and thio-amides vibrations are often considered as signatures of H bond strength. The thermal dependence dynamics of such signatures is studied as an indicator of the bond properties. Finally, in-situ high pressure vibrational measurements demonstrate the role of supramolecular interactions on the mechanical response of hybrid materials to high pressure.

Chalcogenide glasses and more importantly their glass-ceramics counterparts have been an interesting but very peculiar class of thermoelectric materials, with inherently low thermal conductivity (< 0.3 W/m.K). In this study, we report on the fabrication of glasses in the ternary system Cu-As-Te (Cu_xAs_55-xTe₄₅ [5 ≤ x ≤ 20], Cu₁₅As_85-yTe_y [45 ≤ y ≤ 70], and Cu₂₀As_80-yTe_y [45 ≤ y ≤ 65]) by melt-quenching and subsequent spark plasma sintering treatment. Their thermal and structural properties have been studied by differential scanning calorimetry and Raman spectroscopy, leading to give insights into the structural evolution of the glassy matrix. Coupling this information with the analysis of their electrical transport properties allowed us to deepen further our understanding of the compositional effect on their thermoelectric properties, and indirectly how the evolution of their electronic band structure is at play. Despite exhibiting low ZT values by themselves, Cu-As-Te glasses may still be interesting candidates for thermoelectricity through partial crystallization for which knowing the relationship between composition and properties remains essential.

Infrared response on a carbon nanotube is weak because this homonuclear allotrope of carbon does not bear permanent dipoles. Here, we report the discovery of an exaltation of the infrared absorption response in single-walled carbon nanotubes from dye molecule interactions. A study performed on dimethylquaterthiophene confined into the hollow core of single-walled carbon nanotubes or π-stacked at the outer surface of the latter leads to a symmetry breaking, allowing us to probe interactions between both subsystems. The nature of these interactions is discussed taking into account the tube diameter. This new phenomenon opens a new route to detect weak vibrations thanks to a confinement effect.

We report on the preparation of a hybrid nanomaterial made up of 1D filaments of an antiferromagnetic self-assembling bicopper complex encapsulated in polymer nanofibrils. The encapsulation process is achieved through the heterogeneous nucleation of the growth of polymer fibrils obtained by thermoreversible gelation as shown by calorimetry experiments. Neutron scattering experiments confirm that the filaments of a bicopper complex retain their 1D character after encapsulation in the fibrils. Superconducting quantum interference device experiments show that the bicopper complex, originally in the gapped spin state in the 3D bulk mesophase, displays a gapless behavior once encapsulated. Extended absorption fine structure and infrared results further highlight the difference in the molecular arrangement of the bicopper complex between the bulk mesophase and the encapsulated state, which may account for the magnetic behavior. This material, which is largely disordered, differs totally from the usual magnetic systems where this effect is observed only on highly crystalline systems with long-range order. Also, this hybrid material is very easy to prepare from its basic constituents and can be further processed in many ways.

Binary c–T phase diagrams of organogelators in solvent are frequently simplified to two domains, gel and sol, even when the melting temperatures display two distinct regimes, an increase with T and a plateau. Herein, the c–T phase diagram of an organogelator in solvent is elucidated by rheology, DSC, optical microscopy, and transmitted light intensity measurements. We evidence a miscibility gap between the organogelator and the solvent above a threshold concentration, cL. In this domain the melting or the formation of the gel becomes a monotectic transformation, which explains why the corresponding temperatures are nonvariant above cL. As shown by further studies by variable temperature FTIR and NMR, different types of H-bonds drive both the liquid–liquid phase separation and the gelation.