【作者】 杨慧；

【导师】 陈国锋；

【作者基本信息】 河北大学 ， 有机化学， 2024， 硕士

【摘要】 螺烯的高度离域π-电子系统和固有的手性决定了它们独特的光电性能,使得它们在超分子化学、不对称有机合成和有机光电转换器件等领域具有广泛应用前景。利用杂原子替代π共轭骨架内的sp²杂化碳可以改变所得分子的结构,从而产生与碳螺烯不同的手性光学响应和光电性能。杂原子的嵌入不仅扩展了螺烯化学的研究领域,还为设计和合成新型螺烯骨架的有机光电材料提供新的思路。为此,本论文将氮、硼原子嵌入到芳烃分子中,设计合成了不同杂螺烯芳烃分子,论文包含以下两个部分:一是以芘、菲为原料,通过Diels-Alder反应、还原反应和缩合反应合成了三个不对称氮杂螺烯芳烃分子（8,13和19）,通过单晶X-ray衍射确定了13的结构和空间排列。分子8,13的发射峰分别位于470 nm、457 nm,处于蓝光区;分子19的发射峰位于498 nm,处于绿光区。通过电化学测试三个分子的氧化还原过程,获得它们的氧化还原电位,从而计算出HOMO和LUMO能级。通过高压手性色谱柱拆分了分子8,13和19,并利用CD光谱和CPL光谱对它们的手性光学性能进行研究。向8,13和19中加入不同当量的三氟乙酸,荧光呈现淬灭,紫外吸收光谱显示它们的吸收带出现红移,说明螺烯骨架中的氮原子发生质子化从而改变了电子分布。氮杂螺烯衍生物的这些特性,使它们有机会成为潜在的手性光学开关候选分子。二是通过Diels-Alder反应、还原反应和缩合反应合成了扩环的氮杂螺烯芳烃分子25以及利用亲电芳硼化反应合成了硼氮嵌入的杂螺烯芳烃分子29和37,通过单晶X-ray衍射确定了29化合物的结构和空间排列。25的发射峰位于470 nm,处于蓝光区,29的发射峰位于497 nm,处于绿光区而37的发射峰位于588 nm处,处于黄光区。通过电化学测试了25和29的电化学行为,根据第一氧化电位计算出HOMO能级。利用白光分别照射25,29与C₆₀所制成的复合薄膜,表现出明显的且稳定的光电流响应,该光电器件随着光强的增加电流强度也相应的增强。为合成硼氮杂螺烯的分子提供了新思路,有望在有机电子和功能化材料领域得到应用。更多还原

【Abstract】 The highly delocalizedπ-electron system and inherent chirality of helicenes determine their unique photoelectric properties,which make them have broad application prospects in the fields of supramolecular chemistry,molecular recognition,asymmetric organic synthesis,and organic photovoltaic conversion devices.Using heteroatoms to replace the sp² hybrid carbon in theπ-conjugated backbone can change the structure of the resulting molecules,resulting in chiral optical response and photoelectric properties different from those of carbon helicene.The insertion of heteroatoms expands the research field of helicene chemistry and provides new ideas for the design and synthesis of new helicene-based organic optoelectronic materials.Therefore,in this paper,nitrogen and boron atoms are embedded into aromatic molecules to design and synthesize different heterohelicene aromatic molecules.The paper contains the following two parts:Firstly,three asymmetric azepine arenes（8,13 and 19）were synthesized through a series of reactions including Diels-Alder reaction,reduction,and condensation using pyrene and phenanthrene as starting materials.The structure and spatial arrangement of 13 were determined by single-crystal X-ray diffraction.The emission peaks of 8 and 13 are located at470 nm and 457 nm,respectively,which are in the blue region.The emission peak of 19 is located at 498 nm,which is in the green region.The redox potential of the three molecules was obtained by electrochemical test of the redox process of the three molecules,and the HOMO-LUMO levels were calculated.8,13 and 19 were separated by a high-pressure chiral chromatographic column,and their chiral optical properties were studied by CD spectroscopy and CPL spectroscopy.By adding different equivalents of trifluoroacetic acid to 8,13 and 19,the fluorescence was quenched,and the UV absorption spectrum showed a red shift in their absorption bands,indicating that the protonation of the nitrogen atoms in the helicene backbone changed the electron distribution.The CD and CPL spectra were used to test 8,13and 19 under the same conditions,which further verified the protonation process.These properties of azahelicenes derivatives allow them to be potential chiral optical candidate molecules.Secondly,the ring-expanded azahelicenes 25 were synthesized by Diels-Alder reaction,reduction reaction,and condensation reaction,and the boron-nitrogen-embedded heterohelicene 29 and 37 were synthesized by electrophilic arylboration reaction.The structure and spatial arrangement of the 29 compounds were determined by single-crystal X-ray diffraction.The emission peak of 25 is located at 470 nm,which is in the blue region,29is located at 497 nm,which is in the green region,and 37 is located at 588 nm,which is in the yellow region The electrochemical behavior of 25 and 29 was tested by electrochemistry,and the HOMO energy level was calculated according to the first oxidation potential.The 25,29and C₆₀ composite films were irradiated by white light respectively,showing obvious and stable photocurrent response.The photocurrent intensity of the photoelectric device increased with the light intensity.It provides a new idea for the synthesis of boron-nitrogen-embedded heterohelicene,which is expected to be applied in the field of organic electronics and functionalized materials更多还原