Hyper-cross-linked porous polymers (HCPs) are proposed as sorbents for the removal of aromatic volatile pollutants by using toluene as a representative of the BTX family. The hierarchical (micro and meso) porous architecture of the HCPs has been established by N2 physisorption at 77 K while the toluene adsorption capacities were determined by volumetric adsorption at 308 K. The HCPs display very high toluene uptakes, reaching adsorption capacities as high as 154% in weight for the polymer obtained with a tetraphenyl­methane (TPM) and a formaldehyde dimethyl acetal (FDA) ratio of 1/16, whereas only very low uptakes were observed for aliphatic molecules such as n-hexane. HCP materials experience swelling effects evaluated by comparing the volume assessed via N2 physisorption with the volume occupied by toluene molecules in volumetric adsorption experiments. A multispectroscopic approach involving FT-IR and solid-state NMR techniques gave direct proof of the close spatial proximity between the polymeric host framework and guest BTX molecules. Solid-state 1H and 13C NMR spectroscopies have unambiguously identified the presence of CH/π interactions between the guest molecules and the porous framework of the hyper-cross-linked polymers.

Stoichiometric triethylamine in methanol deprotonates the imidazole and yields 98% sub-micrometric ZIF-90 with no residual solvent in the pores.

A full experimental study of the activation energy required for the hitherto unknown neutral 2‐aza‐Cope rearrangement is presented. A kinetic study of the process showed activation energies in the range of 22.91–24.06 kcal/mol, in agreement with a process operating at moderate temperature (70 °C). Calculations at B3LYP/6‐311+G(d,p) and M06‐2X/6‐311+G(d,p) levels of theory considering solvent (dimethyl sulfoxide (DMSO) and toluene) effects (PCM model) predict reaction energy barriers that are in agreement with the values obtained from 1H NMR‐based kinetic experiments. Results obtained by using enantiomerically pure substrates demonstrate that the rearrangement takes place with complete transfer of chirality, in contrast to previously described cationic processes. The effects of solvent and acid catalysis, which converts the process into the more common cationic rearrangement, have also been studied. DFT calculations also predict correctly the acceleration of the process under acid catalysis, estimating energy barriers in the range of 16.80–18.57 kcal/mol.