【作者】 张博；

【导师】 曲红梅； 吴巍；

【作者基本信息】 天津大学 ， 制药工程， 2020， 硕士

【摘要】 1,4-双炔基苯及亚苯基亚乙炔基衍生物是一类具有π-共轭结构的线性低聚物,应用于分子导线、分子传感器、发光二极管和能量传输材料等光电领域,是有机光电材料重要组成部分,具有重要研究价值和应用前景。本文设计了通过茂锆诱导和Sonogashira偶联制备1,4-双（炔基）苯及亚苯基亚乙炔基衍生物的合成路线,合成了一系列新化合物并进行了相关性能测试。本文提出的合成方法具有较高的选择性和收率,以TMS取代炔烃为原料,在茂锆诱导下生成锆杂环戊二烯,然后与第三分子炔烃进行环加成生成TMS取代六取代苯,其经碘化后与相应端炔通过Sonogashira偶联生成相应1,4-双炔基取代苯衍生物2a-2c,Sonogashira偶联的分离收率分别为93%,82%和85%。测试了2a-2c的紫外-可见吸收和荧光光谱、TGA和DSC等性能,对相关测试结果进行了分析和研究。化合物2a脱TMS后生成4,5-二丁基-3,6-双（乙炔基）邻苯二甲酸二甲酯（3）,然后通过Sonogashira偶联反应合成了亚苯基亚乙炔基衍生物4a-4c和5,Sonogashira偶联的分离收率分别为87%,75%,93%和85%。对化合物3、4a-4c和5进行了紫外-可见吸收光谱测试,能隙分别为3.71、3.18、3.24、3.07、2.99e V,表明化合物5的电子跃迁比其他化合物更加容易,即5更有利于载流子传输。荧光光谱测试化合物3、4a-4c和5的发射峰波长分别为358、382、382、402和405nm,其中4a和5的荧光强度相对较强,分别为6043和6707。最后对化合物4a,4b和5进行了TGA和DSC测试,TGA结果表明4a,4b和5初始分解温度T_95%分别为332.2℃、329.8℃和226.7℃,DSC结果表明4a、4b和5的熔化温度分别为164.0℃、177.7℃和181.9℃,说明这些化合物具有良好的热稳定性。以上性能测试结果表明化合物5具有较好的光电性能和热稳定性,有望成为有机光电材料。更多还原

【Abstract】 1,4-Bisynylbenzene and phenyleneethynyl derivatives are a class of linear oligomer withπ-conjugation,which are widely used in photoelectric fields such as molecular wires,molecular sensors,light-emitting diodes and energy transmission materials.It is an important component of organic optoelectronic materials and has very important research value and application prospects.In this paper,a synthetic route for 1,4-bis（alkynyl）benzene and phenyleneethynyl derivatives by zirconocene induction and Sonogashira coupling was designed.A series of new compounds were synthesized and their related properties were tested.The synthesis method proposed in this paper has high selectivity and yields.TMS-substituted alkynes were used as the raw materials to prepare zirconium heterocyclopentadiene by the induction of zirconocene.TMS-substituted hexa-substituted benzenes were synthesized by the cycloaddition with the third molecule alkynes.After iodination,they were reacted with the corresponding terminal alkynes by Sonogashira coupling to prepare the corresponding 1,4-bisalkynyl-substituted benzene derivatives 2a-2c.The separation yields of Sonogashira coupling of 2a-2c were 93%,82%and 85%,respectively.The UV-Vis absorption and fluorescence spectra,TGA and DSC of 2a-2c were tested,and the related test results were analyzed and studied.The TMS groups of 2a were removed to synthesize 4,5-dibutyl-3,6-bis（ethynyl）phthalate dimethyl（3）.Then,the phenyleneethynyl derivatives 4a-4c and 5were synthesized by Sonogashira coupling,and the separation yields of Sonogashira coupling of 4a-4c and 5 were 87%,75%,93%and 85%,respectively.Compounds 3,4a-4c and 5 were tested by ultraviolet-visible absorption spectrum.The energy gap values of 3,4a,4b,4c and 5 were 3.71,3.18,3.24,3.07,2.99e V,indicating that the electronic transition of 5 was easier than other compounds,that is,compound 5 was more conducive to carrier transport.According to the fluorescence spectrum test,the emission peak wavelengths of 3,4a-4c and 5 were 358,382,382,402 and 405nm,among which the fluorescence intensity of 4a and 5 was relatively strong,and the corresponding fluorescence absorption intensity was 6043 and 6707.Finally,the compounds 4a,4b and 5 were tested by TGA and DSC.The results of TGA showed that the initial decomposition temperatures T_95%of 4a,4b and 5 were 332.2℃,329.8℃and226.7℃,indicating that these compounds had good heat stability.The results of DSC showed that the melting temperatures of 4a,4b and 5 were 164.0℃,177.7℃and181.9℃,respectively.The above performance test results showed that compound 5 had good photoelectric properties and thermal stability.It is expected to become a kind of organic optoelectronic material.更多还原