Zhou Qi, Song Kai, Zhang Guanxin, Song Xuwei, Lin Junfeng, Zang Yaping, Zhang Deqing, Zhu Daoben
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, 100190, Beijing, China.
University of Chinese Academy of Sciences, 100049, Beijing, China.
Nat Commun. 2022 Apr 4;13(1):1803. doi: 10.1038/s41467-022-29483-2.
The interface between molecules and electrodes has great impact on charge transport of molecular devices. Precisely manipulating the structure and electronic coupling of electrode-molecule interface at a molecular level is very challenging. Here, we develop new molecular junctions based on tetrathiafulvalene (TTF)-fused naphthalene diimide (NDI) molecules which are anchored to gold electrodes through direct TTF-Au contacts formed via Au-S bonding. These contacts enable highly efficient orbital hybridization of gold electrodes and the conducting π-channels, yielding strong electrode-molecule coupling and remarkably high conductivity in the junctions. By further introducing additional thiohexyl (SHe) anchors to the TTF units, we develop molecular wires with multiple binding sites and demonstrate reversibly switchable electrode-molecule contacts and junction conductance through mechanical control. These findings show a superb electrode-molecule interface and provide a new strategy for precisely tunning the conductance of molecular devices towards new functions.
分子与电极之间的界面对于分子器件的电荷传输具有重大影响。在分子水平上精确操纵电极 - 分子界面的结构和电子耦合极具挑战性。在此，我们基于四硫富瓦烯（TTF）稠合萘二酰亚胺（NDI）分子开发了新型分子结，这些分子通过经由Au - S键形成的直接TTF - Au接触锚定在金电极上。这些接触使得金电极与导电π通道能够进行高效的轨道杂化，在结中产生强的电极 - 分子耦合以及显著高的电导率。通过进一步在TTF单元上引入额外的硫代己基（SHe）锚定基团，我们开发了具有多个结合位点的分子线，并通过机械控制展示了可逆切换的电极 - 分子接触和结电导。这些发现展示了一个卓越的电极 - 分子界面，并为精确调节分子器件的电导以实现新功能提供了一种新策略。
