迫呫吨并呫吨的快速合成及其光电性能

Quick Synthesis and Properties of Peri-Xanthenoxanthene

用微波碳浴法,以2-萘酚为原料,快速合成了迫呫吨并呫吨.优化后的反应条件:醋酸铜(Cu(OAc)2)做氧化剂;Cu(OAc)2与2-萘酚的量的比为3∶1;加热时间为210s左右。在氯仿溶液中,其吸收光谱与发射光谱呈镜面对称关系,最大发射峰波长约为445nm,且呈现较高的荧光量子效率。循环伏安法测得该化合物的最高占有分子轨道(HOMO)和最低未占有分子轨道(LUMO)分别为5.45eV,3.00eV。

We report here the quickly synthesis of peri-xanthenoxanthene using microwave carbon bath for the first time. A specific reactor is assembled to prepare the production with high yield by one step. A 100 mL glass beaker containing a mixture of 2-naphthol and cupric salt is used as reactor and covered by a watch glass. Another 250 mL glass beaker containing powder is served as a thermal bath. The reactor is placed into the bigger beaker. Thermal treatment is accomplished by dielectric loss heating of the carbon powder support using microwave irradiation. The cupric salt, reaction time and content ratio of cupric salt and 2-naphthol have been studied as reaction conditions which influence the yield of peri-xanthenoxanthene. The cupric acetate showed the higher yield than other cupric salt such as CuCl2, CuBr2, CuSO4, Cu（ClO4）2, Cu（NO3 ）2 and Cu（ p-OTs）2. The yield of peri-xanthenoxanthene increases firstly with the increase in the content ratio of Cu （ OAc ） 2 to 2-naphthol ranging from 1 ： 4 to 2 ： 1, then decreases after the content ratio over 4 ： 1. The highest yield （ 86.4% ） is gained at content ratio of 3 ： 1. The 1, 1＇-bi-2-naphthol is the main product if the heating time less than 90 s. The main product changes to peri-xanthenoxanthene over 100 s heating time and the yield of peri-xanthevoxanthene is hardly changed at the heating time was from 150 s to 270 s. It is concluded that 1,1 ＇-bi-2-naphthol is the inter-mediate during the synthesis process from 2-naphthol to peri-xanthenoxanthene. The absorption spectrum and photoluminescence spectrum of peri-xanthenoxanthene are symmetric. The maximum absorption and emission wavelength are 443.6 nm and 445.0 nm respectively. The quantum efficiency is 0.95 in CHCl3 solution, indicating it is a good blue organic electroluminescent materials. The HOMO and LUMO energy levels of peri-xanthenoxanthene are determined by the cyclic vohammetry. The experimental results show that the HOMO and LUMO energy levels are 5.45 eV and 3.00 eV that means a good hole transfer ability. The product begins sublime at 238℃, however, it is stable in the air according to the thermogravimetric analysis. The differential scanning calorimetry （DSC） measurement shows that its glass transition temperature is 133℃. By considering the use of peri-xanthenoxanthene as hole transfer layer in OLED, the lifetime of these diodes would be very short since the planar molecular configuration cannot form stable amorphous membrane.