Sulfide Gels and Films: Products of Non-Oxide Gelation

The preparation of concentrated sols and transparent stiff gels of II-VI semiconductors nanocrystals is reported. A two-step process for the production of cadmium sulfide is reported. Sol stabilization and gelation control are achieved through successive passivation and depassivation of the surface of the nanocrystals which are complexed with thiols. The mechanisms driving the aggregation and the gelation are explained on the basis of NMR and SAXS experiments. Thin films as well as monoliths can be produced. The general principles of the method presented are not restricted to chalcogenide systems and thus enlarge the domain of application of the inorganic sol-gel process.     

Hybrid Xerogel Structure and Molecular Guest Dynamics

A new experimental approach to study the porosity of hybrid organic-inorganic glasses is reported. It relies upon nuclear magnetic resonance observation of molecular guest dynamics. It is shown that in MTEOS xerogels, there exists an interconnected organic-rich network in which organic guests are trapped and can eventually diffuse. The interpore translational diffusion is strongly activated and its spatial extension gives information on the pore connectivity, whose decay is characterized by the interpore jump probability given by the theoretical model.     

NMR study of the magnetic properties of the polymerized phase of Cs1C60

\chem{Cs_{1}C_{60}} . The NMR spectrum allows, when the Magic Angle Spinning (MAS) technique is used, to get information about the electronic structure of this phase, which points out that the spin density is not uniformly distributed on the ball. An estimation of the strength of the quadrupolar effects on is then given, which shows that it is possible to analyse the spin-lattice relaxation time in terms of magnetic effects. A comparison with the of is then justified and allows us to point out the importance of low dimensional antiferromagnetic fluctuations in this compound. We also investigate the nature of the magnetic ground state in : the broadening of the spectra states unambiguously its magnetic nature and a detailed analysis of their shape gives further indications on the antiferromagnetic nature of the magnetic order, which seems characterized by a large amount of disorder. Received: 19 November 1996/Accepted: 19 December 1996     

Xenon-131 surface sensitive imaging of aerogels in liquid xenon near the critical point

In recent years, optically pumped xenon-129 has received a great deal of attention as a contrast agent in gas-phase imaging. This report is about the other NMR active xenon isotope (i.e., xenon-131, S = 32) which exhibits distinctive features for imaging applications in material sciences that are not obtainable from xenon-129 (S = (1/2)). The spin dynamics of xenon-131 in gas and liquid phases is largely determined by quadrupolar interactions which depend strongly on the surface of the surrounding materials. This leads to a surface dependent dispersion of relaxation rates, which can be substantial for this isotope. The dephasing of the coherence due to quadrupolar interactions may be used to yield surface specific contrast for imaging. Although optical pumping is not practical for this isotope because of its fast quadrupolar relaxation, a high spin density of liquid xenon close to the critical point (289 K) overcomes the sensitivity problems of xenon-131. We report the first xenon-131 magnetic resonance images and have tested this technique on various meso-porous aerogels as host structures. Aerogels of different densities and changing levels of hydration can clearly be distinguished from the images obtained.     

Reverse-saturable absorption in aluminophthalocyanine-doped xerogels

Aluminophthalocyanines were encaged in different silica xerogel matrices. Nonlinear reverse-saturable absorption behavior was observed for both nanosecond and picosecond pulse excitation at 532 nm. In order to determine the relaxation paths of the molecules after optical excitation, we measured the evolution of the transmission of a continuous probe beam through the samples following absorption induced by a pump pulse. The transmission recovery was a few tens of microseconds. The fluorescence lifetime was about 10 ns.