莱啉酰亚胺类化合物的邻位C—H键功能化研究进展

Research Progress in Ortho-C—H Bond Functionalization of Rylene Diimides

莱啉酰亚胺是一类重要的功能有机染料.独特的缺电性共轭骨架与优异的光电性质使其成为多环芳烃家族中的重要成员,在有机场效应晶体管、有机光伏器件和生物医学传感等领域具有广阔的应用前景.对莱啉酰亚胺骨架的精准修饰不仅可以有效调控分子能级,还有利于实现分子间的可控组装,是高效创制新型π-分子材料的有效手段.早期,受合成方法的限制,莱啉酰亚胺骨架母核修饰的位点主要局限于电子云密度稍高的湾位,但在该位点引入取代基会扭曲π-平面,不利于π-分子之间的有效堆积.莱啉酰亚胺骨架邻位选择性修饰不影响母核的平面性,近年来受到广泛关注,催生出系列莱啉酰亚胺邻位C—H键功能化的新策略.根据成键类型不同,以苝二酰亚胺和萘二酰亚胺为例,系统总结了莱啉酰亚胺骨架邻位C—H键功能化的方法,以及邻位修饰对莱啉骨架光电性质和组装的影响.

Rylene diimides(RDIs)derivatives are an important class of functional organic dyes.With unique electron-deficient conjugated backbones and excellent photoelectronic properties,these polycyclic aromatic hydrocarbons have wide applications in organic field effect transistors,organic photovoltaic devices,and biomedical sensing.Precise modification of the RDIs skeletons can not only regulate molecular energy levels,but also facilitate controllable assembly betweenπ-molecules,which is an effective means to create newπ-molecular materials.In the early stage,due to the limitation of synthetic methods,only modifications on the bay positions of RDIs can be achieved.However,the introduction of substituents on these sites would distort theπ-plane of RDIs and was not conducive to effectiveπ-stacking between molecules.The selective modifications of RDIs skeletons on the ortho positions do not affect the planarity of the skeletons,which have received much attention in recent years,leading to a series of efficient strategies toward ortho-functionalized RDIs.The methods of ortho-C—H bond functionalization of RDIs such as perylene diimides and naphthalene diimides,and the influence of ortho-modification on the photoelectronic properties and assembly of RDIs derivatives are summarized.