萘基全噻吩双螺旋体的合成与光物理行为研究  

Synthesis and photophysical behaviors of thiophene-based double helices bearing naphthyl groups

作　　者：徐婉 李冰冰 秋帅 汤佳 徐莉[2] 王华[1] Wan Xu;Bingbing Li;Shuai Qiu;Jia Tang;Li Xu;Hua Wang(Institute of Nanoscience and Nanomaterials,Henan University,Kaifeng 475004,China;College of Chemistry and Molecular Sciences,Henan University,Kaifeng 475004,China)

机构地区：[1]河南大学纳米科学与工程研究院,开封475004 [2]河南大学化学与分子科学学院,开封475004

出　　处：《中国科学：化学》2024年第8期1361-1368,共8页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:U2004213);河南省青年自然科学基金(编号:232300420373);中国博士后基金(编号:2023M730951)资助项目。

摘　　要：以“马鞍型”环八四噻吩(COTh)构筑的双螺旋体DH-1为母体化合物,通过Negishi偶联反应制备了双α-萘基与双β-萘基双螺旋体化合物DH-Np-1和DH-Np-2.DH-Np-1和DH-Np-2的晶体结构表明萘基取代位置不同导致分子平面性的显著差异,其中α-萘基、β-萘基与相连的噻吩环的平均二面角分别为73.6°与36.8°,展示出不同的共轭效应,并表现出其吸收和荧光光谱行为存在显著的差异.通过高效液相色谱法对DH-Np-1进行了手性拆分,其对映体(+)-DH-Np-1和(-)-DH-Np-1具有显著的圆二色性与圆偏振发光性质,发光不对称因子达4.9×10^(-3).旋光体(-)-DH-Np-1在固态下250℃加热18 h与在1,2-二氯苯溶液中200℃加热10 h的条件下均未发生外消旋化,表现出较高的旋光稳定性.Based on saddle-shaped cyclooctatetrathiophene(COTh) as building blocks, the double helix DH-1 was employed as the parent molecule for the construction of thiophene-based double helices bearing naphthyl groups via Negishi coupling reactions. The double helices DH-Np-1 and DH-Np-2 bear double α-naphthyl and β-naphthyl groups,respectively. Their crystal structures show that DH-Np-1 and DH-Np-2 lead to significant differences in molecular planarity. The dihedral angles of α-naphthyl, β-naphthyl groups and connected thiophene rings were measured as 73.6° and 36.8°, respectively. The double helices DH-Np-1 and DH-Np-2 exhibited significant differences in both absorption and fluorescence spectra due to the different conjugation effects. The chiral resolution of DH-Np-1 was fulfilled via high-performance liquid chromatography, and the chirality properties of enantiomers(+)-DH-Np-1 and(-)-DH-Np-1showed significant circular dichroism and circularly polarized luminescence properties with luminescence dissymmetry factor of 4.9 × 10^(-3). The high configurational stability of enantiomer(-)-DH-Np-1 was observed without change under the conditions of both 250 ℃ in the solid state for 18 h and 200 ℃ in solution of 1,2-dichlorobenzene for 10 h.

关 键 词：环八四噻吩 双螺旋体 晶体结构 手性 圆偏振发光 

分 类 号：O641.3[理学—物理化学] O734[理学—化学]