Concurrent Covalent and Supramolecular Polymerization

Covalent and supramolecular polymerizations, both of which offer their own unique advantages, have emerged as popular strategies for making artificial materials. Herein, we describe a concurrent covalent and supramolecular polymerization strategy—namely, one which utilizes 1) a bis‐azide‐functionalized diazaperopyrenium dication that undergoes polymeriation covalently with a bis‐alkyne‐functionalized biphenyl derivative in one dimension as a result of a rapid and efficient β‐cyclodextrin(CD)‐accelerated, cucurbit[6]uril(CB)‐templated azide–alkyne cycloaddition, while 2) the aromatic core of the dication is able to dimerize in a criss‐cross fashion by dint of π–π interactions, enabling simultaneous supramolecular assembly, resulting in an extended polymer network in an orthogonal dimension.     

Differences and Commonalities in the Gas‐Phase Reactions of Closed‐Shell Metal Dioxide Clusters [MO2]+ (M=V,Nb, and Ta) with Methane

High‐level electronic structure calculations, in combination with Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometric studies, permit the mechanism by which closed‐shell, “naked” [TaO₂]⁺ brings about C?H bond activation of methane to be revealed. These studies also help to understand why the lighter congeners of [MO₂]⁺ (M=V, Nb) are unreactive under ambient conditions.