量子化学研究不同取代基对六苯并蔻电荷传输性能的影响

应用密度泛函理论在B3LYP/6-311+G(d)、M06-2X/6-311+G(d)、CAM-B3LYP/6-311+G(d)理论水平,分别计算12个不同取代基取代的六苯并蔻分子的电荷传输速率.研究结果显示，采用长程较正泛函CAMB3LYP更适合目标体系的电荷传输性能研究.在六苯并蔻环上，引入6个—CH₃与—CN取代基，得到的六苯并蔻衍生物分子与母体六苯并蔻相比，空穴迁移率相对较大，分别为2.51、0.92 cm²·V^-1·s^-1，可设计为性能优良的p型有机半导体分子；引入6个—SH、—CH2SCH₃及—COOCH₃取代基，得到的3个分子与母体六苯并蔻相比，对分子的电荷传输速率改善较小；引入—SCH₃、—OCH₃、—OH、—NHCH₃、—N(CH₃)2等5个取代基，所得到的5个分子电子迁移速率为空穴迁移速率的1.7～18倍，有望设计成性能优良的n型有机半导体材料.

Quantum chemical study of different substituents effect on the charge transport properties of hexabenzocoronene

In this paper, we used density functional theory (DFT) at the B3LYP/6-311+G(d), M06-2X/6-311+G(d) or CAM-B3LYP/6-311+G(d) level to compute the charge transport rates of twelve hexabenzocoronene molecules substituted with different substituents. The results show that the long-range correction functional CAM-B3LYP is more suitable for the study of the charge transport properties of the target system. Two hexabenzocoronene derivative molecules with six —CH₃ or —CN substituents have relatively large hole mobilities compared with the parent hexabenzocoronene, which are 2.51 cm2·V?1·s?1 and 0.92 cm2·V?1·s?1, respectively. They can be designed as a p-type organic semiconductor. Three hexabenzocoronene derivatives with six —SH, —CH₂SCH₃ or —COOCH₃ substituents have relatively small hole mobilities compared with the parent hexabenzocoronene. The electron mobility of five hexabenzocoronene derivatives with six —SCH₃, —OCH₃, —OH, —NHCH₃, —N(CH₃)₂ substituents is 1.7~18 times that of the hole mobility, and can be designed as n-type organic semiconductors.