A new kind of organic charge transport nanomolecule, 4H-cyclopenta[2,1-b:3,4-b‘]dithiophene-based windmill-shaped nanogrid called WG-CPDT, and its corresponding derivatives substituted by ethynyl, cyano, fluorine and methyl groups at 1-position of CPDT moiety, was designed and studied theoretically. The density functional theory (DFT) was then employed to investigate the molecular structures and electronic properties such as molecular orbitals, ionization potentials (IPs), electron affinities (EAs), reorganization energies (λ). Furthermore, the noncovalent interaction analysis and the normal mode analysis were utilized to estimate the intramolecular weak interactions and the contributions of each vibrational modes to reorganization energies, respectively. The results indicate that WG-CPDT possesses a small reorganization energy in the electron transfer process, and that WG-CPDT is a kind of potential organic electron transport material. This is especially notable when WG-CPDT is modified with cyano on the 1-position of the CPDT moiety and the electron reorganization energies decrease to 0.099 eV. In addition, the delocalization of LUMO near C(sp³) position is consistent with the S···π and C-H···π weak interactions, which favors good electron transport properties. This work provides new insights into a type of bulky macrocycle in charge transport materials.

一种新型的有机电荷传输纳米分子4H-环戊[2,1-b：3,4-b']二噻吩基风车状纳米网格，称为WG-CPDT，及其相应的衍生物被乙炔基，氰基，氟和对CPDT部分1位的甲基进行了设计和理论研究。然后采用密度泛函理论（DFT）来研究分子结构和电子性质，例如分子轨道，电离势（IPs），电子亲和力（EAs），重组能（λ）。此外，非共价相互作用分析和正常模式分析被用来估计分子内的弱相互作用以及每个振动模式对重组能量的贡献。结果表明，WG-CPDT在电子转移过程中具有较小的重组能，WG-CPDT是一种潜在的有机电子传输材料。当在CPDT部分的1位上用氰基修饰WG-CPDT且电子重组能降低至0.099 eV时，这一点尤为明显。此外，LUMO在C（sp ³附近）的离域）的位置与S··π和CH··π的弱相互作用相一致，这有利于良好的电子传输性能。这项工作为电荷输送材料中的一种大体积大循环提供了新的见解。