化学学报 ›› 2013, Vol. 71 ›› Issue (12): 1598-1602.DOI: 10.6023/A13060669 上一篇    下一篇

研究通讯

以芘-炔为基块的共价有机骨架材料的设计合成与表征

张婷婷a, 王海涛a, 马和平b, 孙福兴b, 崔小强a, 朱广山b   

  1. a 吉林大学材料科学系 长春 130012;
    b 吉林大学无机合成与制备化学国家重点实验室 长春 130012
  • 收稿日期:2013-06-27 出版日期:2013-12-14 发布日期:2013-09-16
  • 通讯作者: 崔小强, 朱广山 E-mail:xqcui@jlu.edu.cn;zhugs@jlu.edu.cn
  • 基金资助:

    项目受国家自然科学基金(Nos. 21075051,21275064,20831002)、新世纪优秀人才支持计划(No. NCET-10-0433)、国家重点基础研究发展计划(973 计划,No. 2012CB821700)、重大国际(地区)合作研究(No. 21120102034)资助.

Construction and Characterization of Pyrene-alkyne Based Porous Frameworks

Zhang Tingtinga, Wang Haitaoa, Ma Hepingb, Sun Fuxingb, Cui Xiaoqianga, Zhu Guangshanb   

  1. a Department of Materials Science, Jilin University, Changchun 130012;
    b State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, Jilin University, Changchun 130012
  • Received:2013-06-27 Online:2013-12-14 Published:2013-09-16
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21075051, 21275064, 20831002), Program for New Century Excellent Talents in University (No. NCET-10-0433), National Basic Research Program of China (973 Program, No. 2012CB821700), Major International (Regional) Joint Research Project of NSFC (No. 21120102034).

以四边形基块1,3,6,8-四炔芘和二结点连接体9,10-二溴蒽通过Sonogashira-Hagihara偶联反应构建了一种多孔芳香有机骨架材料PAF-27. 差热重分析结果表明该材料具有一定的热稳定性,在空气中可以稳定到320 ℃,另外,它在一些常见的有机溶剂中能稳定存在,证明了该材料具有一定的化学稳定性. N2吸附结果表明,该材料的比表面积为560 m2/g,平均孔径约为0.63 nm. 由于该材料骨架结构中含有丰富的苯环和炔这样的基团,加上材料本身较大的比表面积和较窄的孔径分布,将在气体的选择分离方面有潜在的应用前景.

关键词: 多孔芳香有机骨架材料, Sonogashira-Hagihara偶联反应, 热稳定性和化学稳定性, 较大的比表面积, 较窄的孔径分布

We report here a porous aromatic framework (PAF-27), which is constructed by a quadrilateral building block 1,3,6,8-tetraethynylpyrene with the linker 9,10-dibromoanthracene via Sonogashira-Hagihara coupling reaction. PAF-27 with plentiful phenyl rings in networks exhibits permanent porosity, high thermal and chemical stabilities, and excellent sorption abilities towards organic chemical pollutants at the saturated vapor pressure and room temperature. The structures of 1,3,6,8-tetrakis(4-(trimethylsilyl)ethynyl)pyrene, 1,3,6,8-tetraethynylpyrene and PAF-27 are firstly studied by 1H NMR and 13C CP/MAS NMR spectroscopy. As shown in the structure of PAF-27, all of the carbon signals with a chemical shift in the range of δ 120~140 are observed, which are related to aromatic carbon atoms of building phenylene groups in the framework. Additionally, the structures with triple-bond linkages have been confirmed by the characteristic resonance of a triple-bonded carbon with a corresponding peak at around δ 90. IR spectra of initial monomer and final product can be found that the characteristic absorption peak for C—Br at 577 cm-1 disappears, which gives an indication for the breakage of the C—Br bonds of 9,10-dibromoanthracene. In addition, the intense absorption peak associated with alkynyl C—H stretching vibration near 3280 cm-1 from the terminal alkyne groups vanishes. Meanwhile, a peak with low intensity is observed near 2169 cm-1 in the final product, which is assigned to the alkyne triple-bond stretching vibration mode. TGA analysis shows that PAF-27 is thermally stable up to 320 ℃ in air condition. In addition, the material also exhibits high chemical stability and cannot dissolve in any common organic solvents. N2 sorption results reveal that the BET surface area of PAF-27 is 560 m2/g and the average pore size is about 0.63 nm. Because of the rich aromatic rings, the large BET and narrow pore distribution, it will display relatively high sorption abilities for gases.

Key words: porous aromatic framework, Sonogashira-Hagihara coupling reaction, high thermal stability and chemical stability, the large BET and narrow pore distribution