The Synthesis of Organic Molecules of Intrinsic Microporosity Designed to Frustrate Efficient Molecular Packing.
The Synthesis of Organic Molecules of Intrinsic Microporosity Designed to Frustrate Efficient Molecular Packing.
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DOI：
10.1002/chem.201504212
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发表时间：
2016-02-12
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影响因子：
--
通讯作者：
McKeown NB
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文献类型：
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作者：
Taylor RG;Bezzu CG;Carta M;Msayib KJ;Walker J;Short R;Kariuki BM;McKeown NB
氟官能化的联苯和三联苯衍生物与儿茶酚官能化的端基之间的有效反应提供了一种获得具有固有微孔性（OMIMs）的大的离散有机分子的途径，所述有机分子仅通过它们的低效填充提供多孔固体。通过改变端基的大小和取代基体积，产生了许多表观BET表面积超过600 m2 g-1的可溶性化合物。 OMIM结构单元产生微孔的效率顺序为螺桨烷>三蝶烯>六苯基苯>螺二芴>萘基=苯基。大体积烃取代基的引入通过进一步降低填充效率而显著增强微孔性。这些结果与以前报道的包装模拟研究的结果是一致的。在三蝶烯单元的桥头位置处引入甲基基团降低了固有微孔性。这可能是由于它们在OMIM结构内的内部位置，使得它们占据空间，但与外围取代基不同，它们不会通过低效堆积而产生自由体积。
Efficient reactions between fluorine‐functionalised biphenyl and terphenyl derivatives with catechol‐functionalised terminal groups provide a route to large, discrete organic molecules of intrinsic microporosity (OMIMs) that provide porous solids solely by their inefficient packing. By altering the size and substituent bulk of the terminal groups, a number of soluble compounds with apparent BET surface areas in excess of 600 m2 g−1 are produced. The efficiency of OMIM structural units for generating microporosity is in the order: propellane>triptycene>hexaphenylbenzene>spirobifluorene>naphthyl=phenyl. The introduction of bulky hydrocarbon substituents significantly enhances microporosity by further reducing packing efficiency. These results are consistent with findings from previously reported packing simulation studies. The introduction of methyl groups at the bridgehead position of triptycene units reduces intrinsic microporosity. This is presumably due to their internal position within the OMIM structure so that they occupy space, but unlike peripheral substituents they do not contribute to the generation of free volume by inefficient packing.