X-band electron spin resonance (ESR) spectra of S(3)(-) 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 g(x) = 2.0016, g(y) = 2.0505, and g(z) = 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 S(3)(-) 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 S(3)(-) molecule having C(2v) 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 S(3)(-) 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 S(3)(-) 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 (2)B(2)-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 S(3)(-) 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.

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Pd(salen) encapsulated in zeolites X and Y is shown t o be a catalyst for the selective hydrogenation of hex-l-ene in the presence of cyclohexene at 25 "C and 400 Torr HZ.

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