Conjugated microporous polymers (CMPs), with rigid π‒conjugated skeletons and tunable microporous structure, have shown great potential as gas storage and sequestration materials, however, the inherent poor solubility of initial building block in the polymerization process always leads to low crosslinking polymers and limited application. Here, in this work, we have designed the flexible@rigid mutualistic symbiosis in two series of CMPs (2D extend truxene and triazatruxene cores, P‒C(‒Et) and P‒N(‒Et). The results demonstrated that rational flexible groups with additional rigid skeletons structure could change the 2D C₃ symmetric building core into 3D steric configuration, which increased the target polymers' BET surface areas more than 3 times and narrowed the microporous width. The optimized molecule structure delivers a high CO₂ uptake ability, 5.8–11.5 wt% for truxene, and 7.8–17.6 wt% for triazatruxene at 273 K and 1.0 bar. Besides, the optimized structures also have superior selectivity of CO₂ when the N₂ or CH₄ still exists in the system. In conclusion, this work provides a fundamental understanding for the design of CMPs for high CO₂ adsorption and separation performances.

具有刚性πpolymers共轭骨架和可调微孔结构的共轭微孔聚合物（CMP）具有巨大的潜力，可作为储气和固存材料，但是，聚合过程中初始结构单元固有的较差的溶解性总是导致低交联聚合物和有限的应用程序。在这里，我们在这项工作中设计了两个系列的CMP（2D延伸的丁烯和三氮杂tru烯核P‒C（‒Et）和P‒N（‒Et））中的flexible @刚性共生共生，结果表明合理的柔性具有附加刚性骨架结构的组可能会更改2D C ₃对称的建筑核心变为3D空间构型，从而将目标聚合物的BET表面积增加了3倍以上，并缩小了微孔宽度。优化的分子结构可提供高的CO ₂吸收能力，在273 K和1.0 bar下，对丁烯的三价氮的含量为5.8-11.5 wt％，对三氮杂tru烯的二价氮含量为7.8-17.6 wt％。此外，当系统中仍然存在N ₂或CH ₄时，优化的结构还具有出色的CO ₂选择性。总之，这项工作为高CO ₂吸附和分离性能的CMP设计提供了基本的了解。