Mechanical force, with its ability to distort, bend, and stretch chemical bonds, is unique in the way it activates chemical reactions. In polymer mechanochemistry, the force is transduced in a directional fashion, and the efficiency of activation depends on how well the force is transduced from the polymer to the scissile bond in the mechanophore (i.e., mechanochemical coupling). We have investigated the effects of regio- and stereochemistry on the rate of force-accelerated retro-Diels-Alder reactions of furan/maleimide adducts. Four adducts, presenting an endo or exo configuration and proximal or distal geometry, were activated in solution by ultrasound-generated elongational forces. A combination of structural (H NMR) and computational (CoGEF) analyses allowed us to interrogate the mechanochemical activation of these adducts. We found that, unlike its thermal counterpart where the reactivity is dictated by the stereochemistry, the mechanical reactivity is mainly dependent on the regiochemistry. Remarkably, the thermally active distal-exo adduct becomes inert under tension due to poor mechanochemical coupling.
A range of fluoride-encapsulated octasilsesquioxane cage compounds have been prepared using the TBAF route. Our studies suggest that whilst it is relatively straightforward to prepare fluoride-encapsulated octasilsesquioxane cage compounds with adjacent sp(2) carbons, leading to a range of aryl and vinyl substituted compounds, the corresponding sp(3) carbon derivatives are more capricious, requiring an electron withdrawing group that can stabilize the cage whilst not acting as a leaving group. Analysis by X-ray crystallography and solution (19)F/(29)Si NMR spectroscopy of R(8)T(8)@F(-) reveal very similar environments for the encapsulated fluoride octasilsesquioxane cages. Migration of a fluoride ion from inside the cage to outside the cage without breaking the T(8) framework and the possibility of encapsulating other anions within silsesquioxane cages have been also investigated.
This paper describes an investigation by ESR methods of the bonding of iron-group impurity ions with the configurations d3, d5, and d8 in LiF, NaF, KF, KMgF3, and KCdF3. The results indicate that π and σ bonding are comparable in magnitude and provide evidence for the relaxation of ligands on to impurity ions in the alkali halides.
The excitations of cobalt fluoride have been studied with the technique of slow-neutron inelastic scattering. A triple-axis crystal spectrometer was used throughout in its constant Q mode of operation. Several of the branches of the phonon spectra were measured and are in reasonable agreement with calculations based on a very simple rigid ion model. The magnetic excitations are of interest because the Co2+ ion has unpaired orbital angular momentum which gives rise to several low-lying energy levels. Excitations have been observed from the ground state to the next three excited states in the antiferromagnetic phase and their dispersion and temperature dependence obtained below, near, and above the Néel temperature. The temperature dependences of the excitations to the different excited states are not the same. The measurements on the magnetic excitation branch of lowest frequency show that, contrary to current theories of magnetism, fairly well-defined magnetic excitations occur to at least 1.5TN Another excitation, which gave a weak scattering intensity, was also observed and it is suggested that this may be associated with a distortion of the crystal structure.
High-pressure experiments, using the piston displacement technique have been performed at temperatures down to that of liquid nitrogen on NH4I, NH4Br, ND4Br, and NH4Cl. For the iodide two new phase transitions under pressure and a new triple point were observed. A new transition and a new triple point were observed in both the bromides; the existence of another transition was confirmed. The role of multipole interactions in causing the transitions is discussed, and on the basis of structural data and the present experiments a generalized phase diagram is presented which describes the gross behavior of the transitions in these substances.
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