Dependence on Film Thickness of Guest-Induced c Perpendicular Orientation in PPO Films.

For poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) films exhibiting nanoporous-crystalline (NC) phases, c⟂ orientation (i.e., crystalline polymer chain axes being preferentially perpendicular to the film plane) is obtained by crystallization of amorphous films, as induced by sorption of suitable low-molecular-mass guest molecules. The occurrence of c⟂ orientation is relevant for applications of NC PPO films because it markedly increases film transparency as well as guest diffusivity. Surprisingly, we show that the known crystallization procedures lead to c⟂ oriented thick (50-300 µm) films and to unoriented thin (≤20 µm) films. This absence of crystalline phase orientation for thin films is rationalized by fast guest sorption kinetics, which avoid co-crystallization in confined spaces and hence inhibit formation of flat-on lamellae. For thick films exhibiting c⟂ orientation, sigmoid kinetics of guest sorption and of thickening of PPO films are observed, with inflection points associated with guest-induced film plasticization. Corresponding crystallization kinetics are linear with time and show that co-crystal growth is poorly affected by film plasticization. An additional relevant result of this study is the linear relationship between WAXD crystallinity index and DSC melting enthalpy, which allows evaluation of melting enthalpy of the NC α form of PPO (ΔHmο = 42 ± 2 J/g).

Molecular Features Behind Formation of α or ß Co-Crystalline and Nanoporous-Crystalline Phases of PPO.

Guest molecular features determining the formation of α and ß phases of poly(2-6-dimethyl-1,4-phenylene) oxide (PPO) are explored by collecting literature data and adding many new film preparations, both by solution casting and by guest sorption in amorphous films. Independently of the considered preparation method, the α-form is favored by the hydrophobic and bulky guest molecules, while the hydrophilic and small guest molecules favor the ß-form. Furthermore, molecular modeling studies indicate that the ß-form inducer guests establish stronger dispersive interactions with the PPO units than the α-form inducer guests. Thus, the achievement of co-crystalline (and derived nanoporous crystalline) α- and ß-forms would result from differences in energy gain due to the host-guest interactions established at the local scale.

Multiple threading of a triple-calix[6]arene host.

The synthesis of the triple-calix[6]arene derivative 6 in which three calix[6]arene macrocycles are linked to a central 1,3,5-trimethylbenzene moiety is reported. Derivative 6 is able to give multiple-threading processes in the presence of dialkylammonium axles. The formation of pseudo[2]rotaxane, pseudo[3]rotaxane, and pseudo[4]rotaxane by threading one, two, and three, respectively, calix-wheels of 6 has been studied by 1D and 2D NMR, DOSY, and ESI-FT-ICR MS/MS experiments. The use of a directional alkylbenzylammonium axle led to the stereoselective formation of endo-alkyl pseudo[n]rotaxane stereoisomers.

A machine learning approach to graph-theoretical cluster expansions of the energy of adsorbate layers.

The accurate description of the energy of adsorbate layers is crucial for the understanding of chemistry at interfaces. For heterogeneous catalysis, not only the interaction of the adsorbate with the surface but also the adsorbate-adsorbate lateral interactions significantly affect the activation energies of reactions. Modeling the interactions of the adsorbates with the catalyst surface and with each other can be efficiently achieved in the cluster expansion Hamiltonian formalism, which has recently been implemented in a graph-theoretical kinetic Monte Carlo (kMC) scheme to describe multi-dentate species. Automating the development of the cluster expansion Hamiltonians for catalytic systems is challenging and requires the mapping of adsorbate configurations for extended adsorbates onto a graphical lattice. The current work adopts machine learning methods to reach this goal. Clusters are automatically detected based on formalized, but intuitive chemical concepts. The corresponding energy coefficients for the cluster expansion are calculated by an inversion scheme. The potential of this method is demonstrated for the example of ethylene adsorption on Pd(111), for which we propose several expansions, depending on the graphical lattice. It turns out that for this system, the best description is obtained as a combination of single molecule patterns and a few coupling terms accounting for lateral interactions.