Heteroatom Effects on Quantum Interference in Molecular Junctions: Modulating Antiresonances by Molecular Design.
Heteroatom Effects on Quantum Interference in Molecular Junctions: Modulating Antiresonances by Molecular Design.
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DOI：
10.1021/acs.jpcc.1c04242
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发表时间：
2021-08-12
期刊：
影响因子：
--
通讯作者：
Bryce MR
中科院分区：
文献类型：
--
作者：
O'Driscoll LJ;Sangtarash S;Xu W;Daaoub A;Hong W;Sadeghi H;Bryce MR
利用量子干涉(QI)控制分子导线中的电荷传输是单分子电子学中一个日益重要的课题。本文利用扫描隧道显微镜-断裂结技术和密度泛函理论计算方法研究了四个分子的单分子电导性质，这些分子是专门为测试扩展的卷曲箭头规则(ECARs)而设计的，用于预测分子结中的QI。具体地说，对于两个新的异构体1-苯基吡咯衍生物，金电极之间的电导途径必须通过一个氮原子：这一新的特征旨在最大化杂原子对电导性质的影响，以前QI的研究并不是这个主题。实验和计算表明，与联苯类似物相比，电导途径中氮原子的存在增加了苯环上锚基位置由对位变为间位的影响。这种影响可以用间位连接的吡咯的破坏性QI(DQI)和对位连接的异构体的位移DQI来解释。这些结果证明了分子设计对反共振的调制，并验证了ECARs作为一种简单的纸笔方法预测QI行为的有效性。这些原理为分子连接中的结构-性质关系提供了新的基本见解，现在可以在一系列不同的杂环分子电子应用中加以利用，例如基于外部门的开关，或在热电设备中。
Controlling charge transport through molecular wires by utilizing quantum interference (QI) is a growing topic in single-molecular electronics. In this article, scanning tunneling microscopy-break junction techniques and density functional theory calculations are employed to investigate the single-molecule conductance properties of four molecules that have been specifically designed to test extended curly arrow rules (ECARs) for predicting QI in molecular junctions. Specifically, for two new isomeric 1-phenylpyrrole derivatives, the conductance pathway between the gold electrodes must pass through a nitrogen atom: this novel feature is designed to maximize the influence of the heteroatom on conductance properties and has not been the subject of prior investigations of QI. It is shown, experimentally and computationally, that the presence of a nitrogen atom in the conductance pathway increases the effect of changing the position of the anchoring group on the phenyl ring from para to meta, in comparison with biphenyl analogues. This effect is explained in terms of destructive QI (DQI) for the meta-connected pyrrole and shifted DQI for the para-connected isomer. These results demonstrate modulation of antiresonances by molecular design and verify the validity of ECARs as a simple “pen-and-paper” method for predicting QI behavior. The principles offer new fundamental insights into structure–property relationships in molecular junctions and can now be exploited in a range of different heterocycles for molecular electronic applications, such as switches based on external gating, or in thermoelectric devices.
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