Order in purely organic network polymers is hard to achieve, as reversible, dynamic covalent bond formation is required. Strategies have focused on thermodynamically controlled transformations, as kinetics would not seemingly favour reversibility. Herein, we report formation of crystalline network polymers under kinetically favoured conditions by using quaternary ammonium salt linked networks. Charged bulky bridges align, even under fast reaction times (20 minutes) if the rotational freedom is granted. Adding vicinal methyl substituents blocks the ordering, hence forming amorphous networks. Raman experiments and SEM images reveal stacking of 2D layers.
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