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International audience; Two-component organogels and xerogels based on a C3-symmetric pyrene-containing gelator have been deeply characterized through a wide range of techniques. Based on the formation of charge transfer complexes, the gelation phenomenon proved to be highly dependent on the nature of the electron poor dopant. This parameter significantly influenced the corresponding gelation domains, the critical gelation concentrations of acceptor dopants, the gel-to-sol transition temperatures, the microstructures formed in the xerogel state and their spectroscopic properties. In particular, titrations and variable-temperature UV-visible absorption spectroscopy demonstrated the key role of donor-acceptor interactions with a remarkable correlation between the phase transition temperatures and the disappearance of the characteristic charge transfer bands. The assignment of these electronic transitions was confirmed through time-dependent density functional theory (TD-DFT) calculations. Eventually, it was shown that the luminescent properties of these materials can be tuned with the temperature, either in intensity or emission wavelength.

Two-component organogels and xerogels based on a C

Through X-ray absorption and emission spectroscopies, the chemical, electronic and structural properties of organic species in solution can be observed. Near-edge X-ray absorption fine structure (NEXAFS) and resonant inelastic X-ray scattering (RIXS) measurements at the nitrogen K-edge of para- aminobenzoic acid reveal both pH- and solvent-dependent variations in the ionisation potential (IP), 1s→π* resonances and HOMO–LUMO gap. These changes unequivocally identify the chemical species (neutral, cationic or anionic) present in solution. It is shown how this incisive chemical state sensitivity is further enhanced by the possibility of quantitative bond length determination, based on the analysis of chemical shifts in IPs and σ* shape resonances in the NEXAFS spectra. This provides experimental access to detecting even minor variations in the molecular structure of solutes in solution, thereby providing an avenue to examining computational predictions of solute properties and solute–solvent interactions.

The synthesis and liquid crystal properties are reported for tri- and tetra-catenar mesogens in which both hydrocarbon and semiperfluorocarbon chains have been incorporated. In the tricatenar mesogens, the lamellar spacing in the smectic C phase of the all-hydrocarbon mesogen almost doubles when the isolated hydrocarbon chain is replaced by a semiperfluorinated chain on account of the localized segregation in different sublayers between the two chain types. In the tetracatenar materials, the replacement of at least one hydrocarbon chain by semiperfluorocarbon chains is sufficient to promote columnar phase formation, but when the molecule has two hydrocarbon chains at one end and two semiperfluorocarbon chains at the other, the requirement for localized phase segregation leads to the formation of a rectangular phase with very large lattice parameters. The juxtaposition of terminal chains of different nature within the same molecular structure thus leads to a reduction in mesophase symmetry and the emergence of more complex supramolecular organization.

NEXAFS-RIXS and home laboratory-based UV-Vis absorption spectroscopy are combined to examine the speciation and electronic structure of para- aminobenzoic acid (PABA) in aqueous solution as a function of pH. DFT and TD- DFT electronic structure calculations reproduce the experimental trends and provide a correlation between the experimental HOMO↔LUMO gap as well as the electronic transitions between molecular orbitals in the non-ionic, anionic and cationic forms of PABA.

Nitrogen K-edge XPS and NEXAFS of the two polymorphic forms of para- aminobenzoic acid (PABA) are significantly different reflecting variation in hydrogen bonding. Alteration in hydrogen bonding at the amino group leads to a shift to high energy for both the XPS N 1s core level and the 3π* NEXAFS resonance with β-PABA. Participation of the amine group in the aromatic system causes the 1π* resonance to be sensitive to the nature of the intermolecular bonding at the para-carboxylic acid group, and a shift to low energy for α- PABA is observed due to hydrogen-bonded carboxylic acid dimer formation. FEFF calculations also successfully reproduce both the energy and intensity variations observed for the σ* shape resonance associated with the C-N bond, with the majority of the decrease in energy observed for b-PABA arising from the longer C-N bond.

Nitrogen K-edge XPS and NEXAFS of the two polymorphic forms of para- aminobenzoic acid (PABA) are significantly different reflecting variation in hydrogen bonding. Alteration in hydrogen bonding at the amino group leads to a shift to high energy for both the XPS N 1s core level and the 3 p * NEXAFS resonance with b -PABA. Participation of the amine group in the aromatic system causes the 1 p * resonance to be sensitive to the nature of the intermolecular bonding at the para -carboxylic acid group, and a shift to low energy for a - PABA is observed due to hydrogen-bonded carboxylic acid dimer formation. FEFF calculations also successfully reproduce both the energy and intensity variations observed for the s * shape resonance associated with the C - N bond, with the majority of the decrease in energy observed for b -PABA arising from the longer C - N bond.

Detailed analysis of the C K near-edge X-ray absorption fine structure (NEXAFS) spectra of a series of saccharides (fructose, xylose, glucose, galactose, maltose monohydrate, α-lactose monohydrate, anhydrous β-lactose, cellulose) indicates that the precise determination of IPs and σ* shape resonance energies is sensitive enough to distinguish different crystalline saccharides through the variations in their average C-OH bond lengths. Experimental data as well as FEFF8 calculations confirm that bond length variations in the organic solid state of 10(-2) Å can be experimentally detected, opening up the possibility to use NEXAFS for obtaining incisive structural information for molecular materials, including noncrystalline systems without long-range order such as dissolved species in solutions, colloids, melts, and similar amorphous phases. The observed bond length sensitivity is as good as that originally reported for gas-phase and adsorbed molecular species. NEXAFS-derived molecular structure data for the condensed phase may therefore be used to guide molecular modeling as well as to validate computationally derived structure models for such systems. Some results indicate further analytical value in that the σ* shape resonance analysis may distinguish hemiketals from hemiacetals (i.e., derived from ketoses and aldoses) as well as α from β forms of otherwise identical saccharides.