Journal
ACS NANO
Volume 8, Issue 7, Pages 6571-6579Publisher
AMER CHEMICAL SOC
DOI: 10.1021/nn501906w
Keywords
on-surface reaction; scanning tunneling microscopy; PAH; porous graphene; hexagonal boron nitride; boronitrene; nanomesh
Categories
Funding
- Swiss National Science Foundation (SNSF) [CRSI20-122703, 149627]
- CSCS (Centro Svizzero di Calcolo Scientifico) [s425]
- Schrodinger computer at the University of Zurich
- ERC AdG Nanograph
- Swiss National Science Foundation [SNF-200021_149627]
- Swiss National Science Foundation (SNF) [200021_149627] Funding Source: Swiss National Science Foundation (SNF)
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Catalytic activity is of pivotal relevance in enabling efficient and selective synthesis processes. Recently, covalent coupling reactions catalyzed by solid metal surfaces opened the rapidly evolving field of on-surface chemical synthesis. Tailored molecular precursors in conjunction with the catalytic activity of the metal substrate allow the synthesis of novel, technologically highly relevant materials such as atomically precise graphene nanoribbons. However, the reaction path on the metal substrate remains unclear in most cases, and the intriguing question is how a specific atomic configuration between reactant and catalyst controls the reaction processes. In this study, we cover the metal substrate with a monolayer of hexagonal boron nitride (h-BN), reducing the reactivity of the metal, and gain unique access to atomistic details during the activation of a polyphenylene precursor by sequential dehalogenation and the subsequent coupling to extended oligomers. We use scanning tunneling microscopy and density functional theory to reveal a reaction site anisotropy, induced by the registry mismatch between the precursor and the nanostructured h-BN monolayer.
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