In Situ Coupling of Single Molecules Driven by Gold‐Catalyzed Electrooxidation. Issue 45 (11th July 2019)

• Record Type: Journal Article
• Authors: Zang, Yaping; Stone, Ilana; Inkpen, Michael S.; Ng, Fay; Lambert, Tristan H.; Nuckolls, Colin; Steigerwald, Michael L.; Roy, Xavier; Venkataraman, Latha
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 45(2019)
• Page Start: 16008
• Page End: 16012
• Publication Date: 2019-07-11
• Subjects: aniline -- azobenzene -- electrocatalysis -- electrooxidation -- single-molecule measurements; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201906215
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A single‐molecule method has been developed based on the scanning tunneling microscope (STM) to selectively couple a series of aniline derivatives and create azobenzenes. The Au‐catalyzed oxidative coupling is driven by the local electrochemical potential at the nanostructured Au STM tip. The products are detected in situ by measuring the conductance and molecular junction elongation and compared with analogous measurements of the expected azobenzene derivatives prepared ex situ. This single‐molecule approach is robust, and it can quickly and reproducibly create reactions for a variety of anilines. We further demonstrate the selective synthesis of geometric isomers and the assembly of complex molecular architectures by sequential coupling of complementary anilines, demonstrating unprecedented control over bond formation at the nanoscale. Abstract : Azobenzene derivatives can be created selectively from anilines through a gold‐catalyzed oxidative coupling that is driven by the local electrochemical potential at a gold STM tip. The products were detected through single‐molecule conductance measurements and compared with azobenzene derivatives prepared ex situ.