Tuning the Organogelating and Spectroscopic Properties of a C3 -Symmetric Pyrene-Based Gelator through Charge Transfer.

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.

Incompatibility-Driven Self-Organization in Polycatenar Liquid Crystals Bearing Both Hydrocarbon and Fluorocarbon Chains.

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 Sensitivity to Bond Lengths in Complex Molecular Materials: A Study of Crystalline Saccharides.

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 ß-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 ß forms of otherwise identical saccharides.

Intermolecular bonding of hemin in solution and in solid state probed by N K-edge X-ray spectroscopies.

X-ray absorption/emission spectroscopy (XAS/XES) at the N K-edge of iron protoporphyrin IX chloride (FePPIX-Cl, or hemin) has been carried out for dissolved monomers in DMSO, dimers in water and for the solid state. This sequence of samples permits identification of characteristic spectral features associated with the hemin intermolecular bonding. These characteristic features are further analyzed and understood at the molecular orbital (MO) level based on the DFT calculations.

Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p-Aminobenzoic Acid.

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.