A Robust Molecular Rectifier Based on Ferrocene-Functionalized Bis(diarylcarbene) on Gold

Abstract

While thiol-based adsorbates have achieved significant success in surface modification and molecular electronics, their thermal and storage instability has hindered long-term commercial viability. Carbene-based thin films offer a promising alternative due to their enhanced stability; however, their molecular electronic properties after postfunctionalization remain to be investigated. In this study, by attaching a ferrocene (Fc) unit to a bis(diarylcarbene)-modified gold surface via carbodiimide coupling, the system exhibits diode behavior with a current rectification ratio of ∼100. This diode behavior is highly temperature-dependent, indicating that hopping is the dominant mechanism for current rectification. Notably, the system demonstrated excellent electrical stability under ambient storage conditions for over 6 months. Our work highlights the potential for designing carbene-based molecular junctions through postmodification and for developing durable functional molecular electronic devices.