The development of polymers of intrinsic microporosity (PIMs) over the last two decades has established them as a distinct class of microporous materials, which combine the attributes of microporous solid materials and the soluble nature of glassy polymers. Due to their solubility in common organic solvents, PIMs are easily processable materials that potentially find application in membrane-based separation, catalysis, ion separation in electrochemical energy storage devices, sensing, etc. Dibenzodioxin linkage, Tröger's base, and imide bond-forming reactions have widely been utilized for synthesis of a large number of PIMs. Among these linkages, however, most of the studies have been based on dibenzodioxin-based PIMs. Therefore, this review focuses precisely on dibenzodioxin linkage chemistry. Herein, the design principles of different rigid and contorted monomer scaffolds are discussed, as well as synthetic strategies of the polymers through dibenzodioxin-forming reactions including copolymerization and postsynthetic modifications, their characteristic properties and potential applications studied so far. Towards the end, the prospects of these materials are examined with respect to their utility in industrial purposes. Further, the structure-property correlation of dibenzodioxin PIMs is analyzed, which is essential for tailored synthesis and tunable properties of these PIMs and their molecular level engineering for enhanced performances making these materials suitable for commercial usage.
Energetic materials containing azoles are appealing in
terms of
their high nitrogen content and presence of functional groups that
can participate in different non-covalent bonding interactions. One
such interesting compound is 4,4′-azobis(1,2,4-triazole) (ATRZ),
which has formidable energetic parameters. Based on the presence of
hydrogen-bond acceptor and metal coordination sites, a number of tailor-made
energetic materials have been derived by employing ATRZ as the molecular
precursor. In this review, we discuss the use of this high-energy
molecular scaffold in the development of different energetic cocrystals,
coordination polymers, and composites and discuss their properties
in the context of state-of-the-art energetic materials.
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