Yu Panpan, Li Yang, Zhao Huijuan, Zhu Lingyun, Wang Yongshuai, Xu Wei, Zhen Yonggang, Wang Xinran, Dong Huanli, Zhu Daoben, Hu Wenping
Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Sciences Tianjin University, Collaborative Innovation Center of Chemical Science, and Engineering, Tianjin, 300072, China.
Beijing National Laboratory for Molecular Science, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
Small. 2021 May;17(20):e2006574. doi: 10.1002/smll.202006574. Epub 2021 Apr 6.
There is very limited repertoire of organic ambipolar semiconductors to date. Electron donor-acceptor alternative stacking is a unique and important binary motif for 1D mixed-stack cocrystals, opening up possibilities for the development of organic ambipolar semiconductors. Herein, four 1D mixed-stack cocrystals using N,N'-bis(perfluorobutyl)-1,7-dicyanoperylene-3,4:9,10-bis(dicarboximide) (PDICNF) as the acceptor and anthracene, pyrene, perylene, and meso-diphenyl tetrathia[22]annulene[2,1,2,1] (DPTTA) as the donors are achieved in a stoichiometric ratio (D:A = 1:1) through solution or vapor processed methods. Their packing structures, energy levels, charge transfer interactions, coassembling behaviors, and molecular orientations are systematically investigated by single-crystal X-ray analysis, absorption spectra, fluorescence quenching, Job's curve plot, and polarized photoluminescence measurements with the help of theoretical calculations. The donor-acceptor alternative stacking direction coincides with the long axis for all the four cocrystals. The field-effect transistors based on Pyrene-PDICNF show the electron mobility up to 0.19 cm V s , which is the highest value among perylene diimide-based cocrystals. Moreover, DPTTA-PDICNF cocrystals possess well-balanced electron and hole mobility with 1.7 × 10 and 2.0 × 10 cm V s respectively due to both hole and electron strong superexchange interactions, shedding light on the design of 1D mixed-stack cocrystals with excellent ambipolar transport behaviors.
迄今为止，有机双极性半导体的种类非常有限。电子供体 - 受体交替堆积是一维混合堆积共晶体独特且重要的二元结构单元，为有机双极性半导体的发展开辟了可能性。在此，通过溶液法或气相法以化学计量比（D:A = 1:1）制备了四种一维混合堆积共晶体，它们以N,N'-双（全氟丁基）-1,7-二氰基苝-3,4:9,10-双（二甲酰亚胺）（PDICNF）作为受体，蒽、芘、苝和内消旋二苯基四硫杂[22]轮烯[2,1,2,1]（DPTTA）作为供体。借助理论计算，通过单晶X射线分析、吸收光谱、荧光猝灭、乔布曲线绘制和偏振光致发光测量等手段，系统地研究了它们的堆积结构、能级、电荷转移相互作用、共组装行为和分子取向。对于所有四种共晶体，供体 - 受体交替堆积方向均与长轴一致。基于芘 - PDICNF的场效应晶体管显示出高达0.19 cm² V⁻¹ s⁻¹的电子迁移率，这是基于苝二亚胺的共晶体中的最高值。此外，由于空穴和电子的强超交换相互作用，DPTTA - PDICNF共晶体分别具有1.7×10⁻³和2.0×10⁻³ cm² V⁻¹ s⁻¹的平衡电子和空穴迁移率，为设计具有优异双极性传输行为的一维混合堆积共晶体提供了思路。
