桥位二级胺基取代的苝二酰亚胺的合成及其能级结构研究

Synthesis and Energy Levels of Perylene Diimide Derivatives with the Substitutions of Secondary Amino Groups at Bay Positions

通过简易的乌尔曼反应,合成出了一系列桥位二级胺基取代的苝二酰亚胺衍生物2a～2d,并对其能级结构进行了表征.紫外-可见光吸收光谱表明,桥位经过二级胺基取代后苝二酰亚胺的带隙变窄,最大吸收峰出现了100 nm以上的红移,从而使吸收范围覆盖到了近红外区.循环伏安测试表明,桥位经过二级胺基取代后的苝二酰亚胺同时呈现出可逆的还原峰和氧化峰,HOMO能级大幅上升,具有双极性半导体特性.初步探讨了桥位吗啡啉基团取代的苝二酰亚胺2d在有机光伏器件中的应用,证明其既可以用作电子受体,也可以用作电子给体.

A series of perylene diimide derivatives 2a～2d with the substitutions of secondary amino groups at bay positions,were synthesized via simple Ullmann reaction,and their energy levels were charac-terized.From the UV-vis absorption spectra,it was found that,after the introduction of secondary amino into the bay position,the band gaps of perylene diimides became narrower,and the maximum absorption peaks were significantly red-shifted while compared to non-substituted parent compound.Thus,their absorption bands extended to the near-IR range.Through cyclic voltammetry,it was disclosed that 2a,2c,and 2d ex-hibited both reversible reduction and oxidation processes,and their HOMO energy levels increased greatly,indicating bipolar semiconductive characteristics.Preliminary investigation of the application of bis-morpholine substituted perylene diimide 2d in organic photovoltaic devices was performed,and the re-sults demonstrated that 2d could be used as both electron acceptor and electron donor.