有机化学 ›› 2021, Vol. 41 ›› Issue (6): 2401-2407.DOI: 10.6023/cjoc202012011 上一篇    下一篇

研究论文

含单一芘基冠状共轭分子的合成、表征和光物理性质

李璟奭a, 庄桂林b, 黄强a, 王进义a, 吴亚宇a(), 杜平武a,*   

  1. a 中国科学技术大学化学与材料科学学院 合肥 230026
    b 浙江工业大学化学工程学院 杭州 310032
  • 收稿日期:2020-12-05 修回日期:2021-02-08 发布日期:2021-02-26
  • 通讯作者: 杜平武
  • 基金资助:
    国家重点研发计划(2017YFA0402800); 国家自然科学基金(21971229); 国家自然科学基金(51925206); 国家自然科学基金(U1932214); 浙江省自然科学基金(LR19B010001)

A Conjugated Molecular Crown Containing a Single Pyrenyl Unit: Synthesis, Characterization, and Photophysical Properties

Jingshi Lia, Guilin Zhuangb, Qiang Huanga, Jinyi Wanga, Yayu Wua(), Pingwu Dua   

  1. a Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026
    b College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032
  • Received:2020-12-05 Revised:2021-02-08 Published:2021-02-26
  • Contact: Pingwu Du
  • Supported by:
    National Key Research and Development Program of China(2017YFA0402800); National Natural Science Foundation of China(21971229); National Natural Science Foundation of China(51925206); National Natural Science Foundation of China(U1932214); Zhejiang Provincial Natural Science Foundation(LR19B010001)

由于独特的结构和物理性质, 大环共轭化合物引起了研究者广泛关注. 报道了含单个芘单元的[7]环对苯基-2,7-芘([7]CPPPy2,7)大环分子的合成方法和光物理性质. 通过含弯曲结构的前驱体和芘的双硼酸酯化底物的Suzuki-Miyanra偶联反应, 加入亚锡酸还原芳构化, 该分子的成功制备被质谱及系列相关核磁共振谱图等表征证实. 新化合物的光物理性质通过紫外-可见光谱等测试方法进一步研究, 其最大紫外吸收峰出现在326 nm, 与理论计算结果相吻合. 在350 nm波长光激发下, 其荧光激发峰值出现在492 nm处. 计算结果表明, 该化合物的应变能为299.17 kJ•mol–1.

关键词: 共轭大环分子, 分子环, 多环芳烃,

Macrocyclic π-conjugated materials have attracted much attention due to their unique structures and physical properties. The synthetic methods and physical properties of a π-extended molecular crown containing a single pyrenyl unit, cyclo[7]paraphenylene-2,7-pyrenylene ([7]CPPPy 2,7), were report. This macrocycle was achieved by a rationally designed Suzuki-Miyanra coupling of a curved precursor and pyrene-2,7-bis(boronate), followed by reductive aromatization with stannous acid, and confirmed by various physical characterizations, such as HR-MS and a series of NMR spectroscopies. The photophysical properties of [7]CPPPy2,7 were further studied by UV-vis spectroscopy and other analysis, and its maximum absorption peak was located at 326 nm, which was consistant with density functional theory (DFT) calculations. The fluorescence emission spectrum of [7]CPPPy2,7 was further studied. Under 350 nm excitation, the emission peak appeared at 492 nm. The computational result indicates the strain energy of [7]CPPPy2,7 is as high as 299.17 kJ•mol–1.

Key words: π-conjugated macrocycle, molecular crown, polyaromatic hydrocarbon, pyrene