Fine‐Tuning the Molecular Design for High‐Performance Molecular Diodes Based on Pyridyl Isomers

• Published in: Angewandte Chemie International Edition 2023-08, Vol.62 (34), p.e202307733-n/a
• Main Authors: Peng, Wuxian, Chen, Ningyue, Wang, Caiyun, Xie, Yu, Qiu, Shengzhe, Li, Shuwei, Zhang, Liang, Li, Yuan
• Format: Article
• Language: English
• Subjects: Charge Transport; Diodes; Electrical junctions; Electrodes; Gallium oxides; Isomers; Leakage current; Molecular Diodes; Molecular electronics; Molecule-Electrode Coupling; Resistors; Self-Assembled Monolayers; Self-assembly
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202307733

Better control of molecule‐electrode coupling (Γ) to minimize leakage current is an effective method to optimize the functionality of molecular diodes. Herein we embedded 5 isomers of phenypyridyl derivatives, each with an N atom placed at a different position, in two electrodes to fine‐tune Γ between self‐assembled monolayers (SAMs) and the top electrode of EGaIn (eutectic Ga−In terminating in Ga2O3). Combined with electrical tunnelling results, characterizations of electronic structures, single‐level model fittings, and DFT calculations, we found that the values of Γ of SAMs formed by these isomers could be regulated by nearly 10 times, thereby contributing to the leakage current changing over about two orders of magnitude and switching the isomers from resistors to diodes with a rectification ratio (r+=|J(+1.5 V)/J(−1.5 V)|) exceeding 200. We demonstrated that the N atom placement can be chemically engineered to tune the resistive and rectifying properties of the molecular junctions, making it possible to convert molecular resistors into rectifiers. Our study provides fundamental insights into the role of isomerism in molecular electronics and offers a new avenue for designing functional molecular devices. Moving the positions of nitrogen atoms in self‐assembled monolayers (SAMs) of phenylpyridyl‐terminated isomers allows the coupling strength between the SAMs and the top electrode to be finely tuned from strong, to modest, to weak coupling. This results in the switching of the isomers from non‐rectifying resistors (rectification ratios, r+=1 at ±1.5 V) to high‐performance molecular diodes (r+=229).