We pressure tune the hydrogen bond in Fe-O-H⋅⋅⋅O-P structural segments of mixed-valence barbosalite (Fe 2+ Fe 3+ 2)(PO4)2(OH)2. Infrared spectroscopy evidences changes in softening of O-H stretch modes and excessive profile broadening onset below 10 GPa. Single-crystal X-ray diffraction shows pseudo-symmetrization of the original monoclinic unit cell concurs with these changes in the O-H vibrational mode. These are considered compelling indicators of proton delocalization onset below 10 GPa as hydrogen bonds are strengthened under pressure. Subsequently in the range 10−30 GPa, Fe Mössbauer spectroscopy discerns Fe 2+ ⇔ Fe 3+ valence fluctuations at proximate cations of the hydrogen bonds. When the original crystal potential at an Fe 2+ site is perturbed by proton delocalization at a ligand, electron exchange is induced along Fe 2+ →L→Fe 3+ pathways (ligand L = O or (OH)-of shared octahedral faces). Thus, (Fe 2+ Fe 3+ 2)(PO4)2(OH)2 under pressure exemplifies the interplay between proton (THz) and electron (MHz) dynamics on two disparate time scales in the same condensed phase.

The synthesis of multifunctional poly(amidoamine)(PAMAM)-based dendrimers containing a cleavable disulfide linkerwithin each armof the dendrimer, together with condensable triethoxysilyl groups on the periphery of the dendrimer, isdescribed. The dendrimers were mixed with bis(triethoxysilyl)benzene and subsequently transformed into silsesquioxanegels or periodic mesoporous organosilicas (PMOs) to generate materials with dendrimers covalently embedded within theinterior of the silsesquioxane networks. Subsequent treatment of the gels with dithiothreitol enabled the core of thedendrimers to be selectively cleaved at the disulfidesite, thus generating thiol functions localised within the pores.The effect of different dendrimer generations on the reactivity of the pendant thiol functions was probed by impregnationwith gold salts, which were reduced to obtain gold nanoparticleswithin the pore networks of the gels and PMOs. The gelsyielded polydisperse gold nanoparticles (2 to 70 nm) with dimensions modulated by the generation of thedendrimer,together with well-defined gold/thiolate clusters with Au...S distances of 2.3 Å. Suchclusters were also observed in the PMOsystem, together with monodispersed gold nanoparticles with diameters comparable to that of the organised pores in thePMO. The role of surface functionalisation in controlling the formation of gold clusters and/or nanoparticles is discusse

We report a complete investigation of the structural, electronic, vibrational, elastic and piezoelectric properties of the P2 1 2 1 2 1 orthorhombic phase in cadmium diiodate (δ-Cd(IO 3) 2) by combining experiments and first-principles based calculations. We revisited the nature of the electronic band gap and suggest an indirect band gap with a value of 4.6 eV. The infrared and Raman responses were measured and the different phonon modes assigned. To date, the δ-Cd(IO 3) 2 piezoelectric response remains unknown. We reported the different mechanisms involved in its piezoelectric response from the density functional perturbation theory. The highest value of the piezoelectric-stress and piezoelectric-strain constants in the zero Kelvin limit is predicted for e 41 =-0.27 C/m 2 and d 41 =-10.32 pC/N. These sizable values associated with the thermal stability (no phase transition up to the thermal decomposition at 550°C) and a relative large electronic band gap make δ-Cd(IO 3) 2 a potential candidate for piezoelectric applications.

Photoluminescence of single-walled carbon nanotubes is monitored at the individual scale by molecule encapsulation into their hollow core. Depending on the electronic character (electron donor or acceptor) of the confined molecule, enhancement or quenching of the photoluminescence intensity is demonstrated. This behavior is assigned to a charge transfer, evidenced by the shift of the Raman G-band, and a correlated Fermi level shift shown by photoemission experiments. Our experimental results are supported by DFT calculations. A consistent picture of the physical interactions taking place in the hybrid systems and their effects on the optical and electronic properties is given. Our results indicate that the electron affinity or ionization potential of the encapsulated molecules and the diameter of the nanotube are relevant parameters to tune the light emission properties of the hybrid systems at the nanoscale.