Targeted synthesis of a large triazine-based [4+6] organic molecular cage: structure, porosity and gas separation

Abstract

Herein, we report the targeted synthesis and solid state assembly of a novel triazine-based [4+6] organic molecular cage. The tetrahedral cage features a large cavity (∼2070 Å(3)), and after desolvation, the resultant material exhibits a high Brunauer-Emmett-Teller surface area of 1181 m(2) g(-1) and also features selective adsorption of CO2 over N2.

Four Simple Structure Carbazole‐Based Conjugated Microporous Polymers with Different Soft Connected Chains

“…The CO 2 /N 2 and the CO 2 /CH 4 selectivities were comparable to other reported materials, such as covalent triazine‐based frameworks (14‐41), polyimides SMPI‐0 (30), dibenzoheterocycle‐functional nanoporous polymeric networks NPTNs (22‐45), ZIF‐78 (10), and Cz‐POFs (4.4‐7.1) . Importantly, PCz–C3–Cz still exhibited high CO 2 /N 2 (33.8) and CO 2 /CH 4 (7.3) selectivity even at 298 K and 1.0 bar, which were higher than P‐1 (4.0),21 triazine‐based cage networks (4.7‐3.9) and TPI‐1‐3@IC (2.0‐11.0) . Attributing to their high selectivity of CO 2 /N 2 and CO 2 /CH 4 , the conjugated microporous polymers (PCz–C n –Cz) would have potential applications in postcombustion CO 2 capture.…”

Covalent triazine polymers using a cyanuric chloride precursor via Friedel–Crafts reaction for CO2 adsorption/separation

“…The calculated CO 2 /N 2 adsorption selectivity for PCTP-1 and PCTP-2 were 46.1 and 31.6, respectively, whereas the corresponding CO 2 /CH 4 selectivities were 15.1 and 19.9, respectively. These PCTPs selectivities were significantly higher than that of previously reported frameworks [55][56][57][58]. The high uptake capacity of CO 2 gas and its high selectivity against N 2 or CH 4 in PCTP-1 was attributed to the quadrupole interaction between the CO 2 molecules and lone pair electrons of the nitrogen atom in the networks as well as the high polarizability of CO 2 gases relative to N 2 or CH 4 , aided by the high surface area of the material.…”

The Chemistry of Porous Organic Molecular Materials

“…[142] Other CO 2 selective POC materials have been reported, including a series of [2+3] amine functionalized organic cages reported by Zhang, which had ideal adsorption CO 2 /N 2 selectivity values up to 138/1, [144,145] although these Zhang cages have lower CO 2 adsorption capacities than the Mastalerz cage. [142] CO 2 /N 2 selectivity has been reported in a flexible propeller shaped [2+3] imine cage, [146] a porphyrin-based imine cage, [147] a triazine-based imine cage, [148] a cube-shaped POC prepared with tris-salicylaldehyde precursors, [149] cryptand-like [2+3] imine cages with pyrrolic units, [150] and a pyrrole-based imine cage. [151] The cube shaped POC reported by Mastalerz et al adsorbed 18.2 wt% of CO 2 at 273 K and 1 bar, and this is among the highest reported CO 2 uptakes for a molecular material.…”

“…[191] The use of POCs as porous building blocks offers a comparable solution to this problem for molecular materials, although in some (rare) cases, self-catenation of organic cages can also occur, [192][193][194] and this does not always destroy porosity, as demonstrated by Mastalerz and co-workers. [195] There are several possible synthetic routes to POCs; imine condensation, [16,22,24,56,144,[146][147][148][196][197][198][199][200][201][202][203][204][205][206] alkyne methasis, [23,194,[207][208][209][210][211][212][213] and boronic ester condensation [122,195,[214][215][216] are the most commonly used (Figure 7a), although there is scope adopt other bond-forming chemistries. [217][218][219] POC synthesis has been discussed in several recent reviews, [6,8,143,…”