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The interest in (micro)porous systems is greater than ever before with microporous polymers finding application in areas such as gas storage/separation and catalysis. In contrast to the vast majority of publications on microporous polymers seeking ever higher values for surface area or uptake capacity for a particular gas, this work presents a means to render a microporous system responsive to electromagnetic stimuli. The incorporation of a diarylethene (DAE) derivative in the backbone of a polymer of intrinsic microporosity (PIM) produces a microporous system that exhibits photochromism as proven by UV–vis absorption and NMR studies. In the resulting DAE-PIM, surface area is not a fixed unalterable property but can be influenced by the external and nondestructive stimulus light in a reversible manner. Furthermore, in combination with Matrimid, free-standing membranes can be produced that display light-switchable diffusivity and permeability for carbon dioxide and oxygen. In this way, material scientists are offered the potential to employ only one system that can assume several states with different properties for each.
A heptazine-based polymer network (HMP-3) with a donor–acceptor (D–A) structure was prepared and tested as catalyst for photocatalytic hydrogen evolution from water. Compared to other heptazine-based materials, which are typically prepared at high temperatures and have recently received much interest as metal-free photocatalysts, the low-temperature protocol applied here allows the defined introduction of organic functional groups within the polymer backbone. The structure of HMP-3 contains alternating heptazine and benzothiadiazole moieties as electron acceptors connected by aminobenzene bridges as electron donors. The resulting material leads to enhanced hydrogen evolution compared to graphitic carbon nitride materials prepared at high temperatures (>500 8C) most probably because of the stabilization of photogenerated charge carriers in the D–A structure.