On-Surface Radical Oligomerisation: A New Approach to STM Tip- Induced Reactions

Over the past decade, on-surface fabrication of organic nanostructures has been widely investigated for the development of molecular electronic devices, nanomachines, and new materials. Here, we introduce a new strategy to obtain alkyl oligomers in a controlled manner using on-surface radical oligomerisations that are triggered by the electrons/holes between the sample surface and the tip of a scanning tunnelling microscope. The resulting radicalmediated mechanism is substantiated by a detailed theoretical study. This electron transfer event only occurs when Vs < -3 V or Vs > + 3 V and allows access to reactive radical species under exceptionally mild conditions. This transfer can effectively ‘switch on’ a sequence leading to formation of oligomers of defined size distribution due to the on-surface confinement of reactive species. Our approach enables new ways to initiate and control