利用平面σ-芳香性增强电子输运能力

doi:10.6023/A24010023

摘要/Abstract

芳香性是有机化学中的重要概念,传统芳香族化合物的芳香性通常源于π电子在环上下平面产生的高度离域,而σ-芳香性则主要源于分子内σ键和轨道重叠,两者均能影响分子的电子传输能力。本文中,我们采用密度泛函理论结合非平衡格林函数(DFT+NEGF)方法对苯、噻吩和呋喃及其衍生物进行了芳香性和电子输运性质的系统研究。计算结果表明,苯、噻吩和呋喃分子的电子输运性质受π-芳香性和σ-芳香性影响,其中σ-芳香性和电子传输正相关,而π-芳香性和电子传输能力成负相关。含有两个芳香环的DB、DT和DF分子的电子传输能力受分子平面化影响较大,DF中呋喃环表现出比DT中噻吩环更大的NICS(1)_zz值。芳香性化合物具有更好的共平面趋势,通过F原子修饰DT 和DF分子产生分子内F•••S和F•••O非共价相互作用的设计策略可以极大增加分子平面性和刚性。同时,含有分子内F•••S和F•••O相互作用的虚拟五元环具有平面σ-芳香性特征,有效促进电子沿F•••S和F•••O路径进行传输,从而提高电子传输能力。本研究有助于进一步理解分子芳香性与电子传输能力之间的内在关系,为未来设计更高效的电子器件提供策略。

关键词: 芳香性, 电子传输, 平面性, 分子内相互作用, 密度泛函理论结合非平衡格林函数

In organic chemistry, aromaticity is a fundamental concept. The aromaticity of traditional aromatic compounds usually comes from the high delocalization of π-electrons on the upper and lower planes of the ring, while σ-aromaticity mainly comes from the intramolecular σ bond and orbital overlap, both of which can affect the electron transport capacity of the molecule. In this study, Density Functional Theory combined with Non-Equilibrium Green's Function (DFT+NEGF) method are used to systematically investigate the aromaticity and electronic transport properties of benzene, thiophene, furan, and their derivatives. The computational results reveal that both π-aromaticity and σ-aromaticity have pronounced effects on molecular electronic transport, where σ-aromaticity shows a positive correlation with electron transmission, whereas π-aromaticity displays a negative correlation. The charge transfer properties of DB, DT and DF molecules containing two aromatic rings are significantly influenced by molecular planarization. Moreover, the furan ring in DF exhibits a larger NICS(1)_zz value than the thiophene ring in DT. Furthermore, aromatic compounds typically exhibit a better coplanar trend. The molecular design strategy involving the modification of DT and DF molecules with F atom generates intramolecular F•••S and F•••O non-covalent interactions, which significantly enhance molecular planarity and rigidity. Meanwhile, the virtual five-membered ring structures containing intramolecular F•••S and F•••O interactions have σ-aromaticity characteristics, effectively promoting electron transport along F•••S and F•••O pathways, thereby improving the electron transport capacity. This research contributes to further understanding of the intrinsic relationship between molecular aromaticity and electronic transport capacity, and provides strategies for the designing more efficient electronic devices in the future.

Key words: aromaticity, electron transport, planarity, intramolecular interaction, DFT+NEGF

引用此文

王治业, 肖博怀. 利用平面σ-芳香性增强电子输运能力[J]. 化学学报, doi: 10.6023/A24010023.

Zhiye Wang, Bohuai Xiao. Utilizing planar σ-aromaticity to enhance electron transport abilities[J]. Acta Chimica Sinica, doi: 10.6023/A24010023.

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