Novel classes of contorted hexabenzocoronenes (c-HBCs) which exhibit a doubly concave configuration were synthesized by using hexabenzocoronene as bridge ligand and diphenylamine/triphenylamine as the redox-active termini. Although the analysis of the crystal structures of tri-di(4-methoxyphenyl)amino-substituted HBC (1), trimethoxy-substituted HBC (3) and tri(triphenylamine)-substituted HBC (4) show that the peripheral modified arylamine groups have a certain influence on the interaction force between molecules, the results of UV–vis absorption and fluorescence emission spectra indicate that these arylamine-modified hexabenzocoronenes have similar photophysical properties, which are primarily regulated by the c-HBC center. Subsequent electrochemical tests found that these compounds have multi-step redox process, and there is a certain degree of overlap between the arylamine and arylamine or between the arylamine and the bridge (c-HBC) during the oxidation process. Combining the UV-vis-NIR spectroelectrochemistry with the density functional theory (DFT) calculations, we further explored the electronic characters of the neutral and one-electron oxidation states of tri-di(4-methoxyphenyl)amino-substituted HBC (1), trimethoxy-substituted HBC (3) and tri(triphenylamine)-substituted HBC (4).

通过使用六苯并二氢呋喃作为桥键配体和二苯胺/三苯胺作为氧化还原活性末端，合成了显示出双凹构型的新型扭曲六苯并氢醌（c-HBC）。尽管分析了三-二（4-甲氧基苯基）氨基取代的六溴环十二烷的晶体结构（1），三甲氧基取代的HBC（3）和三（三苯胺）取代的六溴环十二烷（4）表明，外围修饰的芳基胺基团对分子之间的相互作用力有一定的影响，紫外可见吸收和荧光发射光谱的结果表明，这些芳基胺基修饰的六苯并甲酮具有相似的光物理性质，主要受c- HBC中心。随后的电化学测试发现，这些化合物具有多步氧化还原过程，在氧化过程中，芳基胺与芳基胺之间或芳基胺与桥基（c-HBC）之间存在一定程度的重叠。与密度泛函理论（DFT）计算组合的UV-vis-NIR光谱电化学，我们进一步探讨三-二（4-甲氧基苯基）氨基-取代的HBC的中性和单电子氧化态的电子字符（1），三甲氧基取代的HBC（3）和三（三苯胺）取代的HBC（4）。