摘要
心环烯是一种具有独特碗状结构的分子,修饰了功能基团的心环烯衍生物通常能够表现出比心环烯本身更为突出的物理化学性质.吩噻嗪和吩恶嗪均为具有强给电子性质的分子,其相关衍生物在有机太阳能电池、光电子学和生物医药等领域具有良好的应用前景.该研究通过无金属催化的Ullmann反应将吩噻嗪和吩恶嗪功能基团成功修饰到心环烯边缘,得到2种具有C_(5)对称性且含多种杂原子的新型心环烯衍生物——1,3,5,7,9-五吩噻嗪基心环烯和1,3,5,7,9-五吩恶嗪基心环烯.通过质谱、核磁共振波谱和X-射线单晶衍射等手段对其结构进行表征,并利用紫外-可见吸收光谱对其光物理性质进行研究.结合循环伏安、吸收光谱实验以及密度泛函理论计算讨论了其前线分子轨道能级.研究结果显示该类分子在太阳能电池、主客体化学等方面具有潜在的应用前景.
Corannulene is a molecule with a unique bowl-shaped structure.Corannulene derivatives with modified functional groups usually show more prominent physicochemical properties than pristine corannulene.Phenothiazine and phenoxazine are molecules with strong electron-donating properties and their related derivatives have good application potentials in the fields of organic solar cells,optoelectronics and biomedicine.In this study,the functional groups of phenothiazine and phenoxazine were successfully modified to the rim of the corannulene through a metal-free Ullmann reaction,and two novel corannulene derivatives(named 1,3,5,7,9-pentaphenothiazinylcorannulene and 1,3,5,7,9-pentaphenoxazinylcorannulene)with C_(5) symmetry and variety of heteroatoms were successfully obtained.Their structures were characterized using mass spectrometry,nuclear magnetic resonance spectroscopy,and X-ray single crystal diffraction,and their photophysical properties were studied with ultraviolet-visible absorption spectroscopy.Combining cyclic voltammetry,absorption spectroscopy experiments,and density functional theory calculations,the frontier molecular orbital energy levels were discussed.The research results showed that the two synthesized molecules might have potential applications in solar cells and host-guest chemistry.
作者
曾静
谢晓明
李姝慧
姚阳榕
陈佐长
陈斌文
邓林龙
张前炎
谢素原
郑兰荪
ZENG Jing;XIE Xiaoming;LI Shuhui;YAO Yangrong;CHEN Zuochang;CHEN Binwen;DENG Linlong;ZHANG Qianyan;XIE Suyuan;ZHENG Lansun(State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China)
出处
《厦门大学学报（自然科学版）》
CAS
CSCD
北大核心
2022年第5期786-793,共8页
Journal of Xiamen University：Natural Science
基金
国家自然科学基金(21771152,91961113)。
