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The use of direct arylation polymerization (DArP) as a viable strategy to obtain porous organic polymers (POPs) has not been explored to its full potential. Instead, other strategies (such as conventional cross-coupling reactions) are usually employed to yield POPs that employ expensive organometallic monomers whose syntheses require multiple steps. Herein, using DArP, three fluorinated porous organic polymers (fPOPs: TFPP1 , TFPP2 and TFPP3) were obtained that represent unique examples of triptycene motif containing fluorine rich network polymers. These thermally stable polymers (T d > 400 °C with high char yields at 800 °C) are predominantly microporous with high surface areas (up to 1295 m2/g) and thus satisfy the requirement for facilitating superior adsorption of small gas molecules. The recorded CO 2 , CH 4 , and H 2 uptake capacities of fPOPs are superior than several previously reported fluorinated/non-fluorinated POPs. High CO 2 uptake capacities of fPOPs are due to the incorporation of ample triptycene motifs and polar C–F bonds in the polymeric backbone. Overall, the high thermal stability, surface area and sorption capacities demonstrated by these fluorinated polymers render them potential materials for the applications in capture of CO 2 and storage of CH 4 /H 2. Synthesis of a set of three unique triptycene based fluorinated porous organic polymers via direct C–H arylation and their efficient uptake of CO 2 , CH 4 and H 2. [Display omitted] • Unique report of three triptycene based "fluorinated" porous organic polymers. • Facile polymer syntheses from commercially available fluorinated monomers. • Polymers are microporous with high surface areas (up to 1295 m2/g). • Polymers have high thermal stabilities (T onset up to 582 °C) and (T d up to 626 °C). • Improved CO 2 uptake (upto 160 mg/g) relative to several reported fluorinated POPs. [ABSTRACT FROM AUTHOR]

Coal-fired power plants are the highest contributors to global electricity generation. Flue gases from thermal power plants are rich in carbon dioxide. Thus, thermal plants also contribute substantially to the annual increase in the concentration of atmospheric CO 2 (greenhouse gas) which in turn leads to increased global warming and ocean acidification. Solutions to these problems are either capture of carbon dioxide from flue gas or exploring alternative sources of power generation such as nuclear energy. However, volatile radioactive byproducts produced in nuclear plants need to be arrested by a suitable adsorbent. Herein, for the first time, we report a triptycene-based hypercrosslinked porous polymer (TBHCP-OH) that contains CO 2 -philic groups (–OH and –N N–). It was obtained using a simple Friedel–Crafts alkylation reaction. Mesoporous TBHCP-OH has high CO 2 capture capacity (87.6 mg/g) and excellent iodine vapor uptake capacity (2600 mg/g). This iodine uptake capacity is the highest among all triptycene based polymers reported till date. This may be attributed to the ample supramolecular interactions between arene/heteroatoms (O and N in TBHCP-OH) and iodine. The facile and simple synthesis of TBHCP-OH as well as its ability to efficiently capture pollutants renders it a promising material for environmental remediation. [Display omitted] • Design of a new triptycene based monomer with active CO2-philic (–N N– and –OH) and N2-phobic (azo) groups. • Facile synthesis of a mesoporous triptycene polymer (TBHCP-OH) with azo and phenolic functionalities via knitting strategy. • TBHCP-OH shows high CO 2 uptake of 8.76 wt.% at 273 K and 1 bar pressure which is comparable with monoethanolamine. • TBHCP-OH selectively captures CO 2 over N 2 at 1 bar which improves at higher temperature [273K (23) and 298 K (28)]. • High I 2 vapor adsorption capacity of TBHCP-OH (up to 2600 mg/g) is best among triptycene based polymers. [ABSTRACT FROM AUTHOR]