Control over Molecular Orbital Gating and Marcus Inverted Charge Transport in Molecular Junctions with Conjugated Molecular Wires
Control over Molecular Orbital Gating and Marcus Inverted Charge Transport in Molecular Junctions with Conjugated Molecular Wires
复制标题
DOI：
10.1002/aelm.202200637
复制
发表时间：
2022-11
影响因子：
6.2
通讯作者：
C. Nijhuis;Ziyu Zhang;Francis Adoah;C. Nickle;S. K. Karuppannan;Lejia Wang;Li Jiang;A. Tadich-A.-Tadic
中科院分区：
文献类型：
--
作者：
C. Nijhuis;Ziyu Zhang;Francis Adoah;C. Nickle;S. K. Karuppannan;Lejia Wang;Li Jiang;A. Tadich-A.-Tadic
最近发现，分子结可以被推入电荷传输的Marcus反转区域，但尚不清楚哪些因素是重要的。这篇论文表明，通过微调分子-电极耦合强度和以二茂铁（Fc）（简称S-OPEnFc（n = 1-3））封端的低聚亚苯基乙炔（OPE）线的隧穿距离，可以在正常区和Marcus反转区之间切换分子线上的电荷传输机制。相干隧穿在短分子（n = 1）的结中的电荷传输机制中占主导地位，但对于n = 2或3，氧化还原反应变得重要。通过中断共轭，S-CH 2-OPEnFc，削弱分子-电极相互作用，分子内轨道门控可以发生，将结完全推入Marcus倒置区域。这些结果表明，弱的分子-电极耦合是重要的推动到马库斯反转区的结。
Recently it is discovered that molecular junctions can be pushed into the Marcus Inverted region of charge transport, but it is unclear which factors are important. This paper shows that the mechanism of charge transport across molecular wires can be switched between the normal and Marcus Inverted regions by fine‐tuning the molecule–electrode coupling strength and the tunneling distance across oligophenylene ethynylene (OPE) wire terminated with ferrocene (Fc) abbreviated as S‐OPEnFc (n = 1–3). Coherent tunneling dominates the mechanism of charge transport in junctions with short molecules (n = 1), but for n = 2 or 3 redox reactions become important. By weakening the molecule—electrode interaction by interrupted conjugation, S‐CH2‐OPEnFc, intramolecular orbital gating can occur pushing the junctions completely into the Marcus Inverted region. These results indicated that weak molecule—electrode coupling is important to push junctions into the Marcus Inverted Region.