三重硫杂扭曲多环芳烃的合成与表征  

Synthesis and characterization of a twisted tri-sulfur-doped polycyclic aromatic hydrocarbon

作　　者：丁鹏鹏 谭元植 Peng-Peng Ding;Yuan-Zhi Tan(Department of Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China)

机构地区：[1]厦门大学化学化工学院化学系,厦门361005

出　　处：《科学通报》2021年第10期1250-1256,共7页Chinese Science Bulletin

基　　金：国家自然科学基金(21771155,21721001)资助。

摘　　要：多环芳烃,通常指的是包含两个或两个以上稠和苯环的芳香化合物.多环芳烃具有优良的光、电及组装性能,在有机发光二极管、有机场效应晶体管、有机太阳能光伏电池等领域具有重要的应用前景.在多环芳烃中,杂原子的引入可以调控其电子结构、偶极矩、组装行为等.其中硫杂多环芳烃,由于其在光电转换、有机电子器件方面表现出的优异性质,而被广泛关注.本研究通过对含有3个噻吩环的寡聚苯撑前体,进行氧化脱氢环化,得到了三重硫杂的多环芳烃分子C_(36)S_(3)H_(10)(C_(9)H_(11))_(6).该三重硫杂多环芳烃含有两个五螺烯的结构单元,呈现出扭曲的几何分子结构.扭曲的分子结构阻碍了分子间的π-π堆积,这也通过变浓度的紫外可见吸收光谱表征得以确认.进一步通过荧光及瞬态荧光光谱,对该三重硫杂扭曲多环芳烃的光学特性进行了研究.Polycyclic aromatic hydrocarbons(PAHs)generally refer to aromatic compounds containing two or more fused benzene rings.PAHs have excellent optical,electronic and self-assembly properties,and have important applications in organic light-emitting diodes(OLED),organic field effect transistors(OFET),organic solar photovoltaic cells(OPVC)and other fields.The introduction of heteroatoms to PAHs can adjust the electronic structure,dipole moment,and the self-assembly behavior.Among them,sulfur-doped PAHs have been widely studied.Due to the proper energy level and bonding mode of sulfur atom,the sulfur-doped PAHs have stronger dipole-dipole interactions,electron donating ability,and weakened aromaticity.Sulfur-doped PAHs usually exhibit unique redox characteristics and better hole transporting,so they are widely used as p-type organic semiconductor and electronic donor in photoelectric conversion,and donation unit in donoracceptor conjugated molecules.Doping PAHs with sulfur is mainly through two ways:post-modification and fusing the sulfur-containing heterocyclic unit.On the other hand,regarding the regulation of geometric structure of carbon skeleton,non-hexagonal ring is introduced to transform the molecular structure from planar to curved structure.The structural distortion can be achieved by the peripherial stereo-hindrance.For example,the PAHs containing helicene units have a highly distorted structure,thus showing a unique optical,electric and assembly properties.In order to construct novel PAHs,this article combines heteroatom doping and geometric control of carbon skeleton.A twisted tri-sulfur-doped PAH C_(36)S_(3)H_(10)(C_(9)H_(11))_(6)(molecule 1)was synthesized by oxidative cyclodehydrogenation of an oligophenylene precursor,which contains three thiophene rings.X-ray single crystal diffraction exactly characterized the structure of molecule 1.Because the ring is not completely fused,molecule 1 contains two[5]helicene units,which leads to a twisted molecular structure.In crystalline state,molecule 1 forms dimer

关 键 词：多环芳烃 硫掺杂 扭曲结构 五螺烯 

分 类 号：TQ241[化学工程—有机化工]