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Highly porous photoluminescent diazaborole-linked polymers: synthesis, characterization, and application to selective gas adsorption

机译:高度多孔的光致发光二氮杂硼杂环戊烷连接的聚合物:合成,表征和应用于选择性气体吸附

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摘要

The formation of boron–nitrogen (B–N) bonds has been widely explored for the synthesis of small molecules, oligomers, or linear polymers; however, its use in constructing porous organic frameworks remains very scarce. In this study, three highly porous diazaborole-linked polymers (DBLPs) have been synthesized by condensation reactions using 2,3,6,7,14,15-hexaaminotriptycene and aryl boronic acids. DBLPs are microporous and exhibit high Brunauer–Emmett–Teller surface area (730–986 m2 g−1) which enable their use in small gas storage and separation. At ambient pressure, the amorphous polymers show high CO2 (DBLP-4: 4.5 mmol g−1 at 273 K) and H2 (DBLP-3: 2.13 wt% at 77 K) uptake while their physicochemical nature leads to high CO2/N2 (35–42) and moderate CO2/CH4 (4.9–6.2) selectivity. The electronic impact of integrating diazaborole moieties into the backbone of these polymers was investigated for DBLP-4 which exhibits green emission with a broad peak ranging from 350 to 680 nm upon excitation with 340 nm in DMF without photobleaching. This study demonstrates the effectiveness of B–N formation in targeting highly porous frameworks with promising optical properties.
机译:的硼 - 氮(B-N)键的形成已广泛探索了小分子,低聚物,或线性聚合物的合成;然而,其在构建多孔有机骨架的使用仍然非常稀少。在这项研究中,三个高度多孔diazaborole联聚合物(DBLPs)已通过缩合反应使用2,3,6,7,14,15-hexaaminotriptycene合成和芳基硼酸。 DBLPs是微孔和中表现出高的布鲁诺尔 - 埃米特 - 特勒表面积(730-986平方米G-1),其使它们能够在小的气体贮藏和分离使用。在环境压力下,在无定形聚合物显示出高的CO 2(DBLP-4:4.5毫摩尔G-1在273 K)和H2(DBLP-3:2.13%(重量)在77 K)摄取,而它们的物理化学性质导致高CO 2 / N 2( 35-42)和中度CO 2 / CH 4(4.9-6.2)的选择性。 diazaborole部分集成到这些聚合物的主链的电子影响进行研究用于DBLP-4表现出与宽峰范围从350到在与在DMF 340nm处无漂白激发680nm处的绿色发光。这项研究表明,在与有希望的光学性质靶向高度多孔的框架B-N形成的有效性。

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