二萘并噻咯的合成及性能（英文）

Synthesis and Properties of a Series of Dinaphthosiloles

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°C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。

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-6 H-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＇- binaphthaiene. Direct substitution of two chloride ions from Ph2SiCI2 or Me2SiCI2 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. Differentia 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.