Tunable Symmetry-Breaking-Induced Dual Functions in Stable and Photoswitched Single-Molecule Junctions

Na Xin, Chen Hu, Hassan Al Sabea, Miao Zhang, Chenguang Zhou, Linan Meng, Chuancheng Jia, Yao Gong, Yu Li, Guojun Ke, Xiaoyan He, Pramila Selvanathan, Lucie Norel, Mark A. Ratner, Zhirong Liu*, Shengxiong Xiao*, Stéphane Rigaut*, Hong Guo*, Xuefeng Guo*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

The aim of molecular electronics is to miniaturize active electronic devices and ultimately construct single-molecule nanocircuits using molecules with diverse structures featuring various functions, which is extremely challenging. Here, we realize a gate-controlled rectifying function (the on/off ratio reaches ∼60) and a high-performance field effect (maximum on/off ratio >100) simultaneously in an initially symmetric single-molecule photoswitch comprising a dinuclear ruthenium-diarylethene (Ru-DAE) complex sandwiched covalently between graphene electrodes. Both experimental and theoretical results consistently demonstrate that the initially degenerated frontier molecular orbitals localized at each Ru fragment in the open-ring Ru-DAE molecule can be tuned separately and shift asymmetrically under gate electric fields. This symmetric orbital shifting (AOS) lifts the degeneracy and breaks the molecular symmetry, which is not only essential to achieve a diode-like behavior with tunable rectification ratio and controlled polarity, but also enhances the field-effect on/off ratio at the rectification direction. In addition, this gate-controlled symmetry-breaking effect can be switched on/off by isomerizing the DAE unit between its open-ring and closed-ring forms with light stimulus. This new scheme offers a general and efficient strategy to build high-performance multifunctional molecular nanocircuits.

Original languageEnglish (US)
Pages (from-to)20811-20817
Number of pages7
JournalJournal of the American Chemical Society
Volume143
Issue number49
DOIs
StatePublished - Dec 15 2021

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry

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