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. 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. 含有两个芳香环的联苯二巯基(DB)、联噻吩二巯基(DT)和联呋喃二巯基(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 diphenyl dithiol (DB), dithiophene dithiol (DT) and difuran dithiol (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 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, 2024, 82(5): 520-526.

Zhiye Wang, Bohuai Xiao. Utilizing Planar σ-Aromaticity to Enhance Electron Transport Abilities[J]. Acta Chimica Sinica, 2024, 82(5): 520-526.

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图/表 9

图1. 基于苯、噻吩和呋喃分子衍生物的分子结构

Figure 1. The molecular structures based on benzene, thiophene and furan molecular derivatives

图2. 构建的金-分子-金分子结模型结构

Figure 2. The constructed model structure of Au-molecule-Au molecular junction

图3. 苯(a)、噻吩(b)和呋喃(c)的分子结构和总的NICS(1)zz. 它们的占据π分子轨道及其对应的NICS(1)zz贡献值

Figure 3. The molecular structure of benzene (a), thiophene (b) and furan (c) and total NICS(1)zz. Their occupied π molecular orbitals and their corresponding contribution to NICS(1)zz

图4. (a) 优化的三种分子结构型. (b) 三种分子的透射谱

Figure 4. (a) The optimized configurations of three molecular junctions. (b) The transmission spectra of three molecules

图5. 三个分子的电导与NICS(1)πzz (a)和NICS(1)σzz (b)的函数关系

Figure 5. The conductance values of three molecules as a function of NICS(1)πzz (a) and NICS(1)σzz (b)

图6. (a) 优化的DB、DT和DF分子结构. (b) 计算的电子透射谱

Figure 6. (a) The optimized molecular structures of DB, DT and DF. (b) The calculated electronic transmission spectra

图7. 在DB、DT和DF分子中不同位点修饰后的分子结构

Figure 7. Molecular structures modified at different sites in DB, DT and DF

图8. 分子的电子透射谱, 红色虚线为费米能级

Figure 8. The molecular electronic transmission spectra, and the red dashed line is the Fermi level

图9. DT-F (a), DT-2F (b), DF-F (c)和DF-2F (d)分子的电子传输路径示意图

Figure 9. Schematic diagrams of the electron transport pathways of DT-F (a), DT-2F (b), DF-F (c) and DF-2F (d) molecules

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