邻位取代苝酰亚胺衍生物的合成及其电子迁移率的研究

Preparation of Ortho Substituted Perylene Bisimides Derivatives and Electron Transport Study

摘要:

本文以N,N’-二（3-戊胺）苝酰亚胺为底物，分别经过Ir催化剂直接催化邻位C-H的硼酸酯化和取代反应得到了2,5,8,11位含氯和含溴的苝酰亚胺衍生物3和4，利用1H NMR、13C NMR和HRMS方法对产物进行了表征。通过在苝酰亚胺的邻位引入卤原子后，相对于化合物1，化合物3和4吸收光谱和荧光光谱均发生了蓝移；LUMO能级明显降低，分别为-4.18 eV和-4.16 eV。邻位引入卤原子后化合物3和4仍然具有良好的热稳定性，其失重5%时的温度（Td）均大于370 ℃。利用空间电荷限制电流(SCLC)法测试了它们的电子迁移率，发现卤原子的引入使分子间排列更加有序，其中化合物3的迁移率最高，可以达到3.05 ?10-4 cm2 V-1 s-1。

Abstract:

Perylene bisimides derivatives 3 and 4 were synthesized at the 2, 5, 8, 11-positions of the perylene core under Ir-catalysis. The structure of the compounds were characterized by means of 1H NMR，13C NMR and HRMS．Compared to compound 1 a hypsochromic shift in the absorption and emission is observed for the derivatives 3 and 4, the tetrachloro derivative showing a greater shift than the tetrabromo one. Their LUMO values are -4.18 eV and -4.16 eV, which are significant low than compound 1. The thermogravimetric analysis (TGA) indicates that all of them have good thermal stability with decomposition temperatures more than 370℃. Electron mobilities were measured by the method of space charge limited current (SCLC). By introducing the halo atom at the ortho position, their films become ordered and they exhibit good electron mobilities, which is up to 3.05 ?10-4 cm2 V-1 s-1 for compound 3.