一锅法Suzuki-Heck反应构筑基于4-乙烯基苯硼酸的发光多孔有机聚合物

doi:10.6023/A15010077

摘要/Abstract

多孔有机骨架材料是近年来出现的一类具有较大的比表面积、孔尺寸小于2 nm的多孔有机聚合物材料. 这些材料由较轻质量的C、H、O、N、B等元素组成, 与常规的微孔材料如分子筛和金属-有机骨架化合物相比, 它们具有较低的骨架密度和较高的比表面积等优点. 在本文中, 我们选择4-乙烯基苯硼酸为底物, 通过与芳基卤代物的Suzuki-Heck反应, 发展了一种基于钯催化的一锅法合成发光多孔有机聚合物的新途径. 红外光谱和固体¹³C核磁研究表明, 4-乙烯基苯硼酸在聚合过程中与芳基卤代物之间的Suzuki-Heck反应进行较为完全. 氮气等温吸附曲线表明, 这类材料具有多孔的性质, BET比表面积最高可达552 m²·g^-1. 由于聚合物中存在有较大的共轭基团, 因此具有良好的发光性质. 我们对这些发光有机多孔聚合物在荧光检测硝基化合物方面的应用进行了初步研究, 发现它们对苦味酸(2,4,6-三硝基苯酚)具有良好的选择性检测能力.

关键词: Suzuki-Heck反应, 4-乙烯基苯硼酸, 发光, 多孔有机聚合物, 检测

In recent years the increasing needs of applications have promoted the evolution of porous organic materials (POPs), which can be constructed by copolymerization of organic monomers based on topology chemistry. The advantages of these materials such as excellent physical and chemical stability, low framework density, various structure features, have made them good candidates in gas storage and separation, catalysis, sensors and so on. In this work, a one-pot synthetic strategy has been developed to construct a series of luminescent microporous organic polymers (LMOPs) by the palladium catalyzed Suzuki-Heck cascade coupling reactions of 4-vinylphenylboronic acid with aromatic halides, such as tetrakis(4-bromophenyl)-methane (TBPM), tris(4-iodophenyl)amine (TIPA), 1,1,2,2-tetrakis(4-bromophenyl)ethene (TBPE) and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (TBPT). Through the optimized conditions, the Pd(OAc)₂/(o-tol)₃P catalyst exhibits the highest efficiency in such a system. The FTIR measurements combined with the solid state ¹³C NMR are employed to confirm the existence of the resultant functional groups, which further proves the success of such polymerization. The resultant materials show porous features with the N₂ adsorption-desorption measurements, with the BET surface areas ranging from 274 to 552 m²·g^-1. Furthermore, with the incorporation of vinyl groups, the polymers exhibit visible luminescent feature from blue to yellow. Considering the emission behaviours of these polymers, the selective quenching toward picric acid is studied with the comparison of other nitroaromatic analytes. The results show that LMOP-11 has the highest sensing ability among these polymers. LMOP-12 shows excellent reusable ability towards picric acid. Such a one-pot method for the preparation of aromatic halides with 4-vinylboronic acid provides a simple and efficient synthetic mean to produce luminescent microporous organic framework that could be used in the selective sensing of explosives.

Key words: Suzuki-Heck reaction, 4-vinylphenylbororic acid, luminescent, porous organic polymers, detection

引用此文

孙立波, 梁志强, 于吉红. 一锅法Suzuki-Heck反应构筑基于4-乙烯基苯硼酸的发光多孔有机聚合物[J]. 化学学报, 2015, 73(6): 611-616.

Sun Libo, Liang Zhiqiang, Yu Jihong. One-pot Suzuki-Heck Reaction to Construct Luminescent Microporous Organic Polymers Based on 4-Vinylphenylbororic Acid[J]. Acta Chim. Sinica, 2015, 73(6): 611-616.

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