Thermal analysis of polysiloxanes. II. Thermal vacuum degradation of polysiloxanes with different substituents on silicon and in the main siloxane chain

Thermogravimetric (TG) investigations of various substituted polysiloxanes of the type \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} ({\rm R}_1 {\rm R}_2 {\rm SiO\rlap{--} )}_n $\end{document} have been carried out in vacuo and the activation energies for the depolymerization processes calculated from the resulting thermograms. (R₁ and R₂ are methyl, ethyl, n-propyl, trifluoropropyl, or phenyl.) It is postulated that the activation energy is mainly a function of the inductive effect of the substituent group and that electron-withdrawing groups attached to silicon increase the activation energy, whereas electron-donating groups decrease it. A linear relation is found between the Taft constant σ^* for the substituent on silicon and the calculated activation energy for depolymerization. Product analysis results from isothermal degradations indicate that the degradation mechanism in a silmethylene siloxane polymer and a silethylene-siloxane polymer is very similar to that in polydimethylsiloxanes (PDMS). For the \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} ({\rm R}_1 {\rm R}_2 {\rm SiO\rlap{--} )}_n $\end{document} polymers, the amount of cyclotrisiloxane in the degradation products increases with the size of the substituent on silicon, and it is postulated that the rate of depolymerization is mainly influenced by short-range steric interactions between the substituents on the silicon atoms of the siloxane chain.     

Analysis of the H + D2 reaction mechanism through consideration of the intrinsic reactant polarisation

The effect of reactant polarisation on the dynamics of the title reaction at collision energies up to 1.6 eV is analysed in depth. The analysis takes advantage of two novel theoretical concepts: intrinsic reaction properties and stereodynamical portraits. Exact quantum methods are used to determine the polarisation moments that quantify the intrinsic reactant polarisation at various levels of detail, including or not product state and/or scattering angle resolution. The data is then examined with the aid of stereodynamical portraits, which facilitate the rationalisation of the stereochemical effects that are relevant for the reaction dynamics. This allows for detailed characterisations of the so-called direct and delayed reaction mechanisms.     

A comparison of the effect of rare earth vs Si site doping on the conductivities of apatite-type rare earth silicates

Apatite-type lanthanum silicate (La_9.33Si₆O₂₆) has been attracting significant recent interest due to its high oxide ion conductivity. In this paper, synthesis and conductivity data for a range of doped samples (Mg, Ca, Sr, Ba, B, Ga and Zn) are reported, in particular, to compare the effect of rare earth vs Si site doping. The results show that Ga, B and Zn favour substitution on the Si site, while Ca, Sr and Ba favour La-site substitution. Mg is shown to be an ambi-site dopant, substituting on either site depending on the starting composition. The samples doped on the Si site show higher conductivities than comparable samples doped on the La site, providing further support for the importance of the silicate network in the conduction process, as initially predicted by atomistic modelling studies. For Ga doping on the Si site, the effect of varying the rare-earth size on the conductivities is also reported.     

Progress in crystal structure prediction

The results of the application of a density functional theory method incorporating dispersive corrections in the 2010 crystal structure prediction blind test are reported. The method correctly predicted four out of the six experimental structures. Three of the four correct predictions were found to have the lowest lattice energy of any crystal structure for that molecule. The experimental crystal structures for all six compounds were found during the structure generation phase of the simulations, indicating that the tailor-made force fields used for screening structures were valid and that the structure generation engine, which combines a Monte Carlo parallel tempering algorithm with an efficient lattice energy minimiser, was working effectively. For the three compounds for which the experimental crystal structures did not correspond to the lowest energy structures found, the method for calculating the lattice energy needs to be further refined or there may be other polymorphs that have not yet been found experimentally.     

A mechanophysical phase transition provides a dramatic example of colour polymorphism: the tribochromism of a substituted tri(methylene)tetrahydrofuran-2-one

Background

Derivatives of fulgides have been shown to have interesting photochromic properties. We have synthesised a number of such derivatives and have found, in some cases, that crystals can be made to change colour on crushing, a phenomenon we have termed “tribochromism”. We have studied a number of derivatives by X-ray crystallography, to see if the colour is linked to molecular structure or crystal packing, or both, and our structural results have been supported by calculation of molecular and lattice energies.

Results

A number of 5-dicyanomethylene-4-diphenylmethylene-3-disubstitutedmethylene-tetrahydrofuran-2-one compounds have been prepared and structurally characterised. The compounds are obtained as yellow or dark red crystals, or, in one case, both. In two cases where yellow crystals were obtained, we found that crushing the crystals gave a deep red powder. Structure determinations, including those of the one compound which gave both coloured forms, depending on crystallisation conditions, showed that the yellow crystals contained molecules in which the structure comprised a folded conformation at the diphenylmethylene site, whilst the red crystals contained molecules in a twisted conformation at this site. Lattice energy and molecular conformation energies were calculated for all molecules, and showed that the conformational energy of the molecule in structure IIIa (yellow) is marginally higher, and the conformation thus less stable, than that of the molecule in structure IIIb (red). However, the van der Waals energy for crystal structure IIIa, is slightly stronger than that of structure IIIb – which may be viewed as a hint of a metastable packing preference for IIIa, overcome by the contribution of a more stabilising Coulomb energy to the overall more favourable lattice energy of structure IIIb.

Conclusions

Our studies have shown that the crystal colour is correlated with one of two molecular conformations which are different in energy, but that the less stable conformation can be stabilised by its host crystal lattice.

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Graphical abstract Graphical representation of the structural and colour change in the tribochromic compound (III).