The synthetic control over pore structure remains highly desirable for porous organic frameworks. Here, we present a competitive chemistry strategy, i.e., a systematical regulation on Friedel–Crafts reaction and Scholl coupling reaction through tuning the ratios of monomers. This leads to a series of spirobifluorene-based microporous polymers (Sbf-TMPs) with systematically tuned porosities and N content. Unlike the existing copolymerization strategy by which the synthesized polymers exhibit a monotonic change tendency in the porosities, our networks demonstrate an unusually different trend where the porosity increases first and then decreases with the increasing Ph/Cl ratios for the monomers. This is mainly ascribed to the completion of coexisting reaction routines and the different “internal molecular free volumes” of the repeating units. The as-made networks feature tunable capacities for CO₂ adsorption over a wide range and attractive CO₂/N₂ selectivities. Moreover, these donor–acceptor type frameworks exhibit selective and highly sensitive fluorescence-on or fluorescence-off properties toward volatile organic compounds, which implies their great potential in fluorescent sensors.

中文翻译：

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1,3,5-三嗪基微孔聚合物，孔隙率可调，可用于CO ₂捕获和荧光传感

对于多孔有机骨架，仍然非常希望对孔结构进行综合控制。在这里，我们提出了一种竞争性的化学策略，即通过调节单体的比例对弗里德-克来福特反应和肖尔偶联反应进行系统的调节。这导致了一系列基于螺二芴的微孔聚合物（Sbf-TMPs）具有系统调整的孔隙率和N含量。与现有的共聚策略不同，在现有的共聚策略中，合成的聚合物在孔隙率方面表现出单调变化趋势，我们的网络显示出异常不同的趋势，其中孔隙率先随单体的Ph / Cl比的增加而先增加然后降低。这主要归因于共存反应程序的完成和重复单元的不同“内部分子自由体积”。₂在宽范围内的吸附和有吸引力的CO ₂ / N ₂选择性。此外，这些供体-受体类型的框架对挥发性有机化合物具有选择性和高度灵敏的荧光导通或荧光截止特性，这暗示了它们在荧光传感器中的巨大潜力。