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The molecular mobility of a MOF-5 metal-organic framework was investigated by broadband dielectric spectroscopy. Three relaxation processes were revealed. The temperature dependence of their relaxation rates follows an Arrhenius law. The process observed at lower temperatures is attributed to bending fluctuations of the edges of the cages involving the Zn-O clusters. The processes ("region II") at higher temperatures were assigned to fluctuations of phenyl rings in agreement with the NMR data found by Gould et al. (J. Am. Chem. Soc. 2008, 130, 3246). The carboxylate groups might also be involved. The rotational fluctuations of the phenyl rings leading to the low frequency part of relaxation region II might be hindered either by some solvent molecules entrapped in the cages or by an interpenetrated structure and have a broad distribution of activation energies. The high frequency part of region II corresponds nearly to a Debye-like process: This is explained by a well-defined structure of empty pores.

The rotational molecular dynamics of water confined to layered oxide materials with brucite structure was studied by dielectric spectroscopy in the frequency range from 10(-2) to 10(7) Hz and in a broad temperature interval. The layered double hydroxide samples show one relaxation process, which was assigned to fluctuations of water molecules forming a layer, strongly adsorbed to the oxide surface. The temperature dependence of the relaxation rates has an unusual saddlelike shape characterized by a maximum. The model of Ryabov et al. (J. Phys. Chem. B 2001, 105, 1845) recently applied to describe the dynamics of water molecules in porous glasses is employed also for the layered materials. This model assumes two competing effects: rotational fluctuations of water molecules that take place simultaneously with defect formation, allowing the creation of free volume necessary for reorientation. The activation energy of rotational fluctuations, the energy of defect formation, a pre-exponential factor, and the defect concentration are obtained as main parameters from a fit of this model to the data. The values of these parameters were compared with those found for water confined to nanoporous molecular sieves, porous glasses, or bulk ice. Several correlations were discussed in detail, such as the lower the value of the energy of defect formation, the higher the number of defects. The pre-exponential factor increases with increasing activation energy, as an expression of the compensation law, and indicates the cooperative nature of the motional process. The involvement of the surface OH groups and of the oxygen atoms of the interlayer anions in the formation of hydrogen bonds was further discussed. For the birnessite sample, the relaxation processes are probably overlaid by a dominating conductivity contribution, which is analyzed in its frequency and temperature dependence. It is found that the conductivity of birnessite obeys the characteristics of semiconducting disordered materials. Especially the Barton/Nakajima/Namikawa relationship is fulfilled. Analyzing the temperature dependence of the direct current (dc) conductivity sigma0 in detail gives some hint that sigma0(T) has also an unusual saddlelike form.

The rotational molecular dynamics of water confined to nanoporous molecular sieves of a regular hexagonal (SBA-15) and of a foamlike pore structure was studied by dielectric spectroscopy in the frequency range from 10(-2) to 10(9) Hz and in a broad temperature interval. Two relaxation processes were observed: the process at lower frequencies is related to water molecules forming a layer, which is strongly adsorbed at the pore surface, whereas the relaxation process at higher frequencies is assigned to fluctuations of water molecules situated close to the center of the pore. The relaxation times of the low-frequency process for both materials and of the high-frequency process for the SBA-15 material have an unusual saddlelike temperature dependence, reported here for the first time. To describe this temperature dependence, a model developed for water confined to nanoporous glasses by Ryabov et al. [J. Phys. Chem. B 2001, 105, 1845] was applied, which considers two competing effects. The characteristic features of these two competing processes were compared with those reported for other porous systems.