State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, PR China.
Phys Chem Chem Phys. 2013 Feb 21;15(7):2449-58. doi: 10.1039/c2cp41876b. Epub 2013 Jan 15.
The electronic structure and charge transport property of 9,10-distyrylanthracene (DSA) and its derivatives with high solid-state luminescent efficiency were investigated by using density functional theory (DFT). The impact of substituents on the optimized structure, reorganization energy, ionization potential (IP) and electronic affinity (EA), frontier orbitals, crystal packing, transfer integrals and charge mobility were explored based on Marcus theory. It was found that the hole mobility of DSA was 0.21 cm(2) V(-1) s(-1) while the electron mobility was 0.026 cm(2) V(-1) s(-1), which were relatively high due to the low reorganization energies and high transfer integrals. The calculated results showed that the charge transport property of these compounds can be significantly tuned via introducing different substituents to DSA. When one electron-withdrawing group (cyano group) was introduced into DSA, DSA-CN exhibited hole mobility of 0.14 cm(2) V(-1) s(-1) which was on the same order of that of DSA. However, the electron mobility of DSA-CN decreased to 8.14 × 10(-4) cm(2) V(-1) s(-1) due to the relatively large reorganization energy and disadvantageous transfer integral. The effect of electron-donating substituents was investigated by introducing methoxy group and tertiary butyl into DSA. DSA-OCH(3) and DSA-TBU showed much lower charge mobility than DSA resulting from the steric hindrance of substituents. On the other hand, both of them exhibited balanced transport properties (for DSA-OCH(3), the hole and electron mobility was 0.0026 and 0.0027 cm(2) V(-1) s(-1); for DSA-TBU, the hole and electron mobility was 0.045 and 0.012 cm(2) V(-1) s(-1)) because of their similar transfer integrals for both hole and electron. DSA and its derivatives were supposed to be one of the most excellent emissive materials for organic electroluminescent applications because of their high charge mobility and high solid-state luminescent efficiency.
通过使用密度泛函理论（DFT）研究了具有高固态发光效率的 9,10-二芳基蒽（DSA）及其衍生物的电子结构和电荷输运性质。基于马库斯理论，探讨了取代基对优化结构、重组能、电离势（IP）和电子亲和能（EA）、前沿轨道、晶体堆积、转移积分和电荷迁移率的影响。结果表明，DSA 的空穴迁移率为 0.21 cm(2) V(-1) s(-1)，而电子迁移率为 0.026 cm(2) V(-1) s(-1)，由于重组能低、转移积分高，因此迁移率相对较高。计算结果表明，通过向 DSA 引入不同的取代基，可以显著调节这些化合物的电荷输运性质。当一个吸电子基团（氰基）引入 DSA 时，DSA-CN 的空穴迁移率为 0.14 cm(2) V(-1) s(-1)，与 DSA 相当。然而，由于相对较大的重组能和不利的转移积分，DSA-CN 的电子迁移率降低至 8.14×10(-4) cm(2) V(-1) s(-1)。通过向 DSA 中引入甲氧基和叔丁基研究了供电子取代基的影响。与 DSA 相比，DSA-OCH(3) 和 DSA-TBU 的电荷迁移率要低得多，这是由于取代基的空间位阻所致。另一方面，由于它们的空穴和电子迁移率相似（对于 DSA-OCH(3)，空穴和电子迁移率分别为 0.0026 和 0.0027 cm(2) V(-1) s(-1)；对于 DSA-TBU，空穴和电子迁移率分别为 0.045 和 0.012 cm(2) V(-1) s(-1)），因此它们都表现出平衡的输运性质。由于具有高电荷迁移率和高固态发光效率，DSA 及其衍生物有望成为有机电致发光应用中最优秀的发光材料之一。
