Photoinduced oxygen transfer and double-linkage isomerism in a cis-(NO)(NO2) transition-metal complex by photocrystallography, FT-IR spectroscopy and DFT calculations

Photocrystallographic experiments show that laser exposure of crystals of [Ru(bpy)2(NO)(NO2)](PF6)2 at 90 K produces a double isonitrosyl-nitrito linkage isomer and provide the detailed geometry of the metastable species generated. The analysis indicates that the isomerization is accomplished through an intramolecular redox reaction involving oxygen transfer from the nitro to the nitrosyl group. At 200 K only a single (nitrito) linkage isomer is formed with a U-shaped conformation of the nitrito group rather than the Z conformation observed at 90 K. A mechanism for the isomerization is proposed based on the crystallographic results and FTIR data collected at low temperatures during the isomerization process. The study presents the first structural evidence for double linkage isomerization in transition-metal complexes.     

Trinuclear gold(I) triazolates: a new class of wide-band phosphors and sensors

A new cyclic gold(I) triazolate trimer, [Au(3,5-i-Pr2Tz)]3 (1), exhibits fully overlapping aurophilically bonded dimer-of-trimer units that lead to multiple phosphorescence bands in both the solid state and solution. The conformation of the hexanuclear unit exhibits reversible interconversion between C2 and D3 effective symmetries, depending on the crystal temperature or solution concentration, the variation of which leads to isoemissive and isosbestic points. Solutions of 1 exhibit remarkable quenching properties that demonstrate molecular recognition with high selectivity and hypersensitivity for some reagents, as influenced by protonation via Br?nsted acids, pi intercalation, and/or energy transfer. The quenched phosphorescence of 1 by acetic acids can be regenerated by NEt3.     

Diffusion of n-pentane in the zeolite ZK5 studied by high-temperature configuration-space exploration

The extremely slow diffusion of the molecule n-pentane caused by the hopping from cage-to-cage in zeolite ZK5 has been investigated by transition state theory (TST). Such slow diffusion cannot be accessed by usual molecular dynamics simulation techniques. The calculation of the partition function ratio needed for TST was enabled by a recently developed method, the so-called high-temperature configuration-space exploration (HTCE). Dynamical corrections for recrossing events have also been taken into account. The obtained intra-zeolite self-diffusion constant between 247 and 317 K of 10⁻¹⁶–10⁻¹⁵ m² s⁻¹ falls in the range of 10⁻¹⁸–10⁻¹⁵ m² s⁻¹ observed experimentally. The calculated energetic barrier between two neighboring cages of 29 kJ mol⁻¹ is in good agreement with that of 28 ± 5 kJ mol⁻¹ obtained from NMR measurement.     

Adsorption of CO2 and N2 in Na–ZSM-5: effects of Na+ and Al content studied by Grand Canonical Monte Carlo simulations and experiments

Zeolite crystals with cations present, such as ZSM-5, are widely used for gas sequestration, separations, and catalysis. One possible application is as an adsorbent to separate CO₂ from N₂ in flue gas mixtures. Typically, the zeolite framework is of a SiO₂ composition, but tetravalent Si atoms can be replaced with trivalent Al atoms. This change in valence creates a charge deficit, requiring cations to maintain the charge balance. Experimental studies have demonstrated that cations enhance adsorption of polar molecules due to strong electrostatic interactions. While numerous adsorption studies have been performed for silicalite-1, the all-silica form of ZSM-5, fewer studies on ZSM-5 have been performed. Grand Canonical Monte Carlo simulations were used to study adsorption of CO₂ and N₂ in Na–ZSM-5 at T = 308 K, which is ZSM-5 with Na⁺ counter-ions present. The simulations suggest that a lower Si/Al ratio (or higher Na⁺ and Al content) substantially increases adsorption at low pressures. At high pressures, however, the effect of the Al substitutions is minor, because the Al^?/Na⁺ sites are saturated with guest molecules. Similarly, a lower Si/Al ratio also increases the isosteric heat of adsorption at low loading, but the isosteric heats approach the silicalite-1 reference values at higher loadings. Comparison of simulations and experimental measurements of the adsorption isotherms and isosteric heats points to the importance of carefully considering the role of charge on the Na⁺ cations, and suggest that the balancing cations in ZSM-5, here Na⁺, only have partial charges.     

Contribution to poly(m-xylylene adipamide) characterization: Hydrolysis,condensation, and oxidation in the melt

PAmXD,6 [poly(m-xylylene adipamide)] was processed using a Brabender plastograph at 30 rpm and at 265 ± 5°C. The evolution of the M_n versus mixing time determined from solution viscosity and chain end concentrations measurements shows that PAmXD,6 undergoes hydrolysis or condensation reactions depending on its initial molecular mass. Lower masses undergo condensation while higher masses undergo hydrolysis. The determination of water concentration in the melt during mixing time confirmed that this behavior is related to an equilibrium constant which was estimated at 500 ± 100. For a mixing period shorter than 20 min, a good correspondence was observed between M_n values determined either by chain end concentrations or by solution viscosity. However, for a mixing period longer than 20 min, discrepancy between M_n values using both methods witnesses the probable appearance of oxidative degradation of PAmXD,6. Mechanisms adapted from the established oxidation reactions of PA6 and PA6,6 are proposed to justify the PAmXD,6 behavior. Those reactions could explain the slight yellowing of PAmXD,6 during its processing. It was also shown that the PAmXD,6 Brabender plastograph mixing torque (30 rpm, 265 ± 5°C) is linearly related to M_n in a log/log diagram. © 1996 John Wiley & Sons, Inc.     

Supramolecular solids as a medium for single-crystal-to-single-crystal E/Z photoisomerization: kinetic study of the photoreactions of two Zn-coordinated tiglic acid molecules

[Zn(TA)2(H2O)2] (H-TA=tiglic acid) has been embedded in a framework composed of CECR (CECR=C-ethylcalix[4]resorcinarene) molecules to examine its E-->Z photoisomerization in a periodic framework. The photoisomerization of tiglic acid in CECR-[Zn(TA)2(H2O)2]4 H2O proceeds without the [2+2]-dimerization reaction that often occurs in crystals of uncomplexed analogues, and without breakdown of the crystal lattice that frequently occurs in neat crystals. The two Zn-coordinated TA molecules are located in different size cavities. The rate constants of the isomerization reaction are strongly affected by the size of the reaction cavity. Analysis of the temperature dependence of the reaction rates and the occupancies in the final photostationary state shows that the activation energies and the standard enthalpies of activation are dependent on the difference between the reaction cavities. This is the first quantitative diffraction study of solid-state E/Z isomerization of a metal-coordinated ligand in a periodic host environment.