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X-band electron spin resonance (ESR) spectra of S3- radicals in ultramarine analog (pigment) prepared from zeolite A and maintaining the original structure of parent zeolite were recorded in the temperature range of 4.2–380 K. Electron spin echo experiments (echo detected ESR, electron spin-lattice relaxation, and spin echo dephasing) were performed in the temperature range of 4.2–50 K. The rigid lattice g factors are gx=2.0016, gy=2.0505, and gz=2.0355, and they are gradually averaged with temperature to the final collapse into a single line with g=2.028 above 300 K. This is due to reorientations of S3- molecule between 12 possible orientations in the sodalite cage through the energy barrier of 2.4 kJ/mol. The low-lying orbital states of the open form of S3- molecule having C2v symmetry are considered and molecular orbital (MO) theory of the g factors is presented. The orbital mixing coefficients were calculated from experimental g factors and available theoretical orbital splitting. They indicate that the unpaired electron spin density in the ground state is localized mainly (about 50%) on the central sulfur atom of S3- anion radical, whereas in the excited electronic state the density is localized mainly on the lateral sulfur atoms (90%). A strong broadening of the ESR lines in directions around the twofold symmetry axis of the radical S3- molecule (z-axis) is discovered below 10 K. It is due to a distribution of the S–S–S bond angle value influencing mainly the energy of the 2B2-symmetry MO. This effect is smeared out by molecular dynamics at higher temperatures. A distribution of the g factors is confirmed by the recovery of the spin system magnetization during spin-lattice relaxation measurements, which is described by a stretched exponential function. Both the spin-lattice relaxation and electron spin echo dephasing are governed by localized phonon mode of energy of about 40 cm-1. Thus, the anion-radical S3- molecules are weakly bonded to the zeolite framework, and they do not participate in the phonon motion of the host lattice because of their own local dynamics. [ABSTRACT FROM AUTHOR]

Abstract: Zeolite losod prepared with tetrabutylammonium hydroxide was applied as matrix for sulfur anion-radicals thermally generated from precursors (elemental sulfur and alkalis or alkaline oligosulfides). We hoped that large los cages could favor formation and stabilization of big radicals (e.g. red ). The products with maintained LOS structure, however, always showed light green or blue coloration (due to and radicals) and bigger radicals never were detected (EPR). It is likely that the sulfur radicals in the products occupy rather eri cages in LOS structure, whereas the large los cages do not accommodate any radicals, because several of them could stay there and subsequently recombine to ordinary oligosulfides. Some reduction of los cage size by means of Cs or K cations resulted in a degradation of LOS structure. Introduction of sulfur compounds already during the losod crystallization disturbed formation of LOS structure. [Copyright &y& Elsevier]

Abstract: The aim of the work was to collect information concerning boundary effects which are suspected in α-alanine dosimeters consisted of powdered microcrystalline α-alanine and binders. In our experiments the conventional binders were replaced by molecular sieves (MS). MS are inorganic porous materials (host structures) with well organized and uniform intra-crystalline pore systems of nano-scale size. The guest molecules can be either physically adsorbed on very large inner MS surface, or chemically bound to the active sites. They can be also encapsulated inside the intracrystalline cavities. The EPR spectra of gamma irradiated dl-α-alanine supported on NaY, CeY, SOD, mordenite, ZSM-5 and ALPO4-5 were very similar to that one observed for irradiated microcrystalline dl-α-alanine. In the case of alanine supported on HY an initial EPR spectrum was different and only after some weeks it made resemble to the well known quintet observed in microcrystalline samples. In sodalites synthesized in the presence of dl-α-alanine EPR signal appeared in non-irradiated sample was very low and structureless. The irradiated sample showed a distinct spectrum which was quite different from that one observed for crystalline dl-α-alanine. [Copyright &y& Elsevier]

Abstract: The colored (greenish) products analogous to ultramarine obtained from zeolite A, cancrinite and erionite by means of high-temperature (500–800°C) treatment of zeolites mixed with elemental sulfur and alkalis can maintain the original structure of the parent zeolite under certain preparation conditions. The ESR spectra of samples recorded at room temperature always indicate the presence of radicals S3 − (the blue chromophore). The spectra of samples prepared from zeolites recorded at 77K exhibit additional signals that could be assigned to the yellow chromophore (the radical S2 −) encapsulated inside the β or ε-cages. It is remarkable that in the case of products with preserved cancrinite structure, where the S2 − radicals are encapsulated inside the ε-cages, the above signals are visible already at room temperature. It may result from retarded mobility of these species in small cancrinite cages. [Copyright &y& Elsevier]

Imidazole (Im) introduced into the channels of H-MFI zeolites (with diverse framework Si/Al) shows remarkably enhanced proton conductivity in a broad temperature range (303–393 K), which increased with Im loading. Some conductivity raise is already noticed after its introduction into slilicalite-1 (i.e. SiO 2) due to escalated Im dispersion and subsequently enhanced mobility inside the channels. The increase, however, becomes much more spectacular for the Im composites based on H-forms of aluminosilicate MFI zeolite matrices. It results from additional beneficial interaction of the guest Im with the zeolite acid sites, particularly OH groups, acting as additional proton carriers. Nevertheless, there is no straight correlation between the number of acid sites and the proton conductivity. It seems that the strong Lewis acid sites, contrary to Broensted centers, hinder the conduction, because of firm bonding the Im molecules and reducing their motion. Thus, both kind of sites compete with each other. The highest conduction noticed for the composites based on the H-zeolite with Si/Al = 50 results not so much from pronounced contribution of Broensted centers, but rather from the small number of Lewis sites which are relatively weak. Both Grotthuss and vehicle conductivity modes could be considered. Image 1 • Anhydrous proton conductors. • Imidazole entrapped in H-zeolites MFI with various Si/Al. • Impact of acid sites on composite conductivity. [ABSTRACT FROM AUTHOR]

Abstract Imidazole entrapped in H-forms of FAU zeolites with various Si/Al ratios (1, 4, 40) exhibit high and stable proton conductivity (up to ∼10−3 S/cm) in a broad range of temperatures (293–393 K). The conductivity increases with temperature and imidazole loading. The number and strength of zeolite acid sites (resulting from various Si/Al) influence markedly the conductivity of composites. The samples based on zeolites with low Si/Al (1) show markedly higher conduction than these supported on the matrix with medium Si/Al (4), regardless of very similar number of the acid OH groups. The strong acid OH groups in zeolite with Si/Al = 4 result in protonation and immobilization of adsorbed imidazole, which reduce their mobility and subsequently the conduction. The low siliceous with weaker acid sites protonate imidazole and form a chain of H-bonds effective in proton propagation. Almost neutral high silica matrix provides a high mobility of dispersed imidazole, due to weak mutual interaction. The overloaded samples indicate a phase transition effect at elevated temperature due to melting of extra-matrix imidazole, which is reflected in dramatic increase in conductivity. Graphical abstract Image 1 Highlights • Proton conductivity of imidazole entrapped in H-forms of faujasites. • Role of imidazole loading, phase transition at high temperature. • Influence of Si/Al on efficiency and mechanism of conduction. [ABSTRACT FROM AUTHOR]

X-ray, UV−vis, FT-infrared, Raman, continuous wave, and pulsed ESR spectroscopy were applied to characterize pigments prepared at 500 °C under vacuum or in air from mixtures of zeolite A (LTA) with sulfur (40 wt %) and anhydrous sodium sulfide (Na2/S = 0.1−0.4). The samples maintained the LTA structure. Sample color results from an S3−absorption band and the shoulder of a UV band. The fingerprint and asymmetric stretch region of the IR spectra show that the pigments synthesized in air have more disordered structures. The S2−/S3−ratio was estimated from Raman spectra. The ESR spectra of S3−radicals show the existence of several phases visible as five different ESR components. Two components dominate: ideal [Na4S3−]3+clusters and clusters existing in a disordered environment. The samples synthesized in air show a substantial distortion of local structure. Synthesis in vacuum leads to products containing about 20% of the ordered crystalline phase. [ABSTRACT FROM AUTHOR]