Chin. J. Org. Chem. ›› 2018, Vol. 38 ›› Issue (5): 1119-1125.DOI: 10.6023/cjoc201710017 Previous Articles     Next Articles

Special Issue: 有机超分子化学合辑



张卫杰a, 徐莉b, 宋金生a, 马志英a, 王华a   

  1. a 河南大学纳米材料工程研究中心 开封 475004;
    b 河南大学化学化工学院 开封 475004
  • 收稿日期:2017-10-16 修回日期:2018-02-08 发布日期:2018-02-11
  • 通讯作者: 马志英,;王华,;
  • 基金资助:


Synthesis of Saddle-Shaped Cyclooctatetrathiophene-Triazine Derivatives and Their Aggregation Induced Emissions (AIE) Properties

Zhang Weijiea, Xu Lib, Song Jinshenga, Ma Zhiyinga, Wang Huaa   

  1. a Research Center for Nanomaterials, Henan University, Kaifeng 475004;
    b College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004
  • Received:2017-10-16 Revised:2018-02-08 Published:2018-02-11
  • Contact: 10.6023/cjoc201710017;
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21672053, 21672054, 21703055), and the Innovation Scientists and Technicians Troop Construction Projects of Henan Province (No. C20150011).

With saddle-shaped cyclooctatetrathiophene (COTh) and 1, 3, 5-triazine as building blocks, three derivatives bearing one, two and three COTh units are synthesized via Kumada-typed reaction. Theoretical calculations indicate that the two absorption peaks in long wavelength region are derived from intramolecular charge transfer (CT) absorption. 2, 4- Di(methoxyl)-6-(5, 8, 11-tris(trimethylsilyl)cycloocta [1, 2-b:4, 3-b':5, 6-b":8, 7-b'"]tetrathiophen-2-yl)-1, 3, 5-triazine (1), 2-meth- oxyl-4, 6-di(5, 8, 11-tris(trimethyl-silyl)cycloocta [1, 2-b:4, 3-b':5, 6-b":8, 7-b'"]tetrathiophen-2-yl)-1, 3, 5-triazine (2) and 2, 4, 6-tris- (5, 8, 11-tris(trimethylsilyl)cycloocta [1, 2-b:4, 3-b':5, 6-b":8, 7-b'"]tetrathiophen-2-yl)-1, 3, 5-triazine (3) exhibit intramolecular charge transfer (ICT) state emission peaked in region of 560~570 nm in solution at room temperature, and give both local emission of COTh peaked at 400 nm and ICT state emission peaked in region of 480~500 nm in rigid solution at 77 K. In tetrahydrofuran (THF)-H2O binary solvent system, compounds 1, 2 and 3 show typical aggregation induced emissions (AIE), which may be controlled by mechanism of restriction of intramolecular rotations (RIR) and restriction of intramolecular vibration (RIV). Crystal structure of 1 shows that intramolecular two rings of triazine and its linked thiophene are planar. There are strong C-C interactions between intermolecular rings of triazine and thiophene, which restrict the intramolecular rotation between triazine and thiophene rings. Such intermolecular C-C interactions are helpful to decrease the process of non-irradiative decay and increase AIE emission.

Key words: cyclooctatetrathiophene, 1, 3, 5-triazine, crystal structure, aggregation induced emission