物理化学学报 >> 2017, Vol. 33 >> Issue (6): 1253-1260.doi: 10.3866/PKU.WHXB201702212

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二萘并噻咯的合成及性能

曲红梅1,*(),种泽鹏1,陈旭2,门奕灿1,申海蛟1   

  1. 1 天津大学化工学院,系统生物工程教育部重点实验室,天津300072
    2 天津金新材科技有限公司,天津300384
  • 收稿日期:2016-12-21 发布日期:2017-05-19
  • 通讯作者: 曲红梅 E-mail:ququhongmei@126.com
  • 基金资助:
    国家自然科学基金(21102099)

Synthesis and Properties of a Series of Dinaphthosiloles

Hong-Mei QU1,*(),Ze-Peng CHONG1,Xu CHEN2,Yi-Can MEN1,Hai-Jiao SHEN1   

  1. 1 Key Laboratory of Systems Bioengineering (Ministry of Education), Tianjin University, Tianjin 300072, P. R. China
    2 Tianjin Kingsrial S & T Company, Limited, Tianjin 300384, P. R. China
  • Received:2016-12-21 Published:2017-05-19
  • Contact: Hong-Mei QU E-mail:ququhongmei@126.com
  • Supported by:
    the National Natural Science Foundation of China(21102099)

摘要:

合成了一类新的二萘并噻咯类化合物,它们分别是6,6-二甲基-1,2,3,4,8,9,10,11-八丙基二萘并噻咯、6,6-二甲基-1,2,3,4,8,9,10,11-八丁基二萘并噻咯、6,6-二苯基-1,2,3,4,8,9,10,11-八丙基二萘并噻咯和6,6-二苯基-1,2,3,4,8,9,10,11-八丁基二萘并噻咯。合成以炔烃为原料,在二氯二茂锆的诱导作用下生成锆杂环戊二烯,再与卤代苯发生偶联反应得到二碘萘,两分子二碘萘经正丁基锂锂化之后又可以反应生成一分子联萘,最后联萘与硅杂物反应得到不同取代基的二萘并噻咯类化合物。此合成方法不仅收率高,而且工艺简单。之后我们又采用核磁以及质谱对这几个分子进行了表征,采用紫外-可见光谱测试、荧光测试、循环伏安测试、热重分析测试以及高斯计算,对它们的光学性能、电化学性能、稳定性等进行了测试。实验结果表明它们有着相似的光吸收带以及很低的HOMO值(-5.50 eV)。它们的热分解温度都在300℃左右,表明它们有良好的热稳定性。最后,我们用6,6-二甲基-1,2,3,4,8,9,10,11-八丁基二萘并噻咯做为发光层制作了电致发光器件,该器件可以发明亮的蓝紫光。

关键词: 二萘并噻咯, 偶联反应, 锂化反应, 循环伏安, 热重分析, 有机电致发光器件

Abstract:

Siloles constitute an important emerging class of photoluminescent materials. A series of compounds consisting of silole cores and fused naphthalene were synthesized and characterized:6, 6-dimethyl-1, 2, 3, 4, 8, 9, 10, 11-octapropyl-6H-dinaphtho[2, 3-b:2', 3'-d]silole, 1, 2, 3, 4, 8, 9, 10, 11-octabutyl-6, 6-dimethyl-6H-dinaphtho[2, 3-b:2', 3'-d]silole, 6, 6-diphenyl-1, 2, 3, 4, 8, 9, 10, 11-octapropyl-6H-dinaphtho[2, 3-b:2', 3'-d]silole, and 1, 2, 3, 4, 8, 9, 10, 11-octabutyl-6, 6-diphenyl-6H-dinaphtho[2, 3-b:2', 3'-d]silole. These dinaphthalene-fused siloles were synthesized from diiodonaphthalene, which was prepared by a direct coupling method. Subsequent reaction in the presence of n-butyllithium yielded 3, 3'-diiodo-2, 2'-binaphthalene. Direct substitution of two chloride ions from Ph2SiCl2 or Me2SiCl2 with 3, 3'-dilithio-2, 2'-binaphthalene then yielded the multi-substituted silole. Nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry were used to characterize the structures of the siloles. Their optical and electronic properties were investigated using ultraviolet-visible absorption spectroscopy, photoluminescence spectroscopy, cyclic voltammetry, and density functional theory calculations. The dinaphthalene-fused siloles exhibited similar absorption and emission peaks. Their deep highest occupied molecular orbital level at approximately -5.5 eV indicated that they were chemically stable. Differential scanning calorimetry and thermogravimetric analysis indicated that the siloles were stable up to 309℃. A multilayer electroluminescent device was fabricated using 1, 2, 3, 4, 8, 9, 10, 11-octabutyl-6, 6-dimethyl-6H-dinaphtho[2, 3-b:2', 3'-d]silole as a light-emitting layer. The resulting device produced bright blue emission, indicating that these siloles may be suitable materials in organic light-emitting devices.

Key words: Dinaphthosilole, Coupling reaction, Lithiation reaction, Cyclic voltammetry, Thermogravimetric analysis, Organic electroluminescent device

MSC2000: 

  • O649