Tang Xiao-Dan
College of Geo-exploration Science and Technology, Jilin University, Changchun, Jilin, 130026, People's Republic of China; Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, Jilin, People's Republic of China.
J Mol Graph Model. 2017 Sep;76:535-542. doi: 10.1016/j.jmgm.2017.06.017. Epub 2017 Jun 23.
By Means of Marcus electron transfer theory, the charge transport properties of tetraazapentacene (4N-PEN) derivatives were systematically explored. The reorganization energies were studied by both adiabatic potential-energy surfaces and normal mode analysis. The charge diffusion constants were evaluated from the random walk simulation. From the perspective of homology modeling, a selected 4N-PEN derivative without experimental crystal structure was built into three kinds of possible packing modes with reference to its relative analogues and then fully optimized. The calculated results show that the charge transport property for the same kind of systems strongly depends on the packing mode, and the π···stacking is more beneficial for electron transport of 4N-PEN derivatives. Meanwhile, the 4N-PEN derivatives have larger electron transfer integrals and lower energy levels of the lowest unoccupied molecular orbitals as well as smaller electron reorganization energies, which provides a three-in-one advantage for electron transport. Fascinatingly, the data obtained from the hopping and band models both suggest that the 4N-PEN derivatives have the intrinsic property of electron transport. Thus, the 4N-PEN derivatives have the potential for preparing n-type organic semiconductors.
借助马库斯电子转移理论，系统地探究了四氮杂并五苯（4N - PEN）衍生物的电荷传输性质。通过绝热势能面和简正模式分析研究了重组能。通过随机游走模拟评估了电荷扩散常数。从同源建模的角度，参考其相关类似物，将一种无实验晶体结构的选定4N - PEN衍生物构建成三种可能的堆积模式，然后进行完全优化。计算结果表明，对于同一类体系，电荷传输性质强烈依赖于堆积模式，并且π···堆积对4N - PEN衍生物的电子传输更有利。同时，4N - PEN衍生物具有较大的电子转移积分、较低的最低未占据分子轨道能级以及较小的电子重组能，这为电子传输提供了三位一体的优势。有趣的是，从跳跃模型和能带模型获得的数据均表明4N - PEN衍生物具有电子传输的内在性质。因此，4N - PEN衍生物具有制备n型有机半导体的潜力。
