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On‐Surface Decarboxylation Coupling Facilitated by Lock‐to‐Unlock Variation of Molecules upon the Reaction

Shaoshan Wang, Zhuo Li, Pengcheng Ding, Cristina Mattioli, Wujun Huang, Yang Wang, André Gourdon, Ye Sun, Mingshu Chen, Lev Kantorovich, Xueming Yang, Federico Rosei, Miao Yu

2021Angewandte Chemie International Edition14 citationsDOIOpen Access PDF

Abstract

On-surface synthesis (OSS) involving relatively high energy barriers remains challenging due to a typical dilemma: firm molecular anchor is required to prevent molecular desorption upon the reaction, whereas sufficient lateral mobility is crucial for subsequent coupling and assembly. By locking the molecular precursors on the substrate then unlocking them during the reaction, we present a strategy to address this challenge. High-yield synthesis based on well-defined decarboxylation, intermediate transition, and hexamerization is demonstrated, resulting in an extended and ordered network exclusively composed of the newly synthesized macrocyclic compound. Thanks to the steric hindrance of its maleimide group, we attain a preferential selection of the coupling. This work unlocks a promising path to enrich the reaction types and improve the coupling selectivity hence the structual homogeneity of the final product for OSS.

Topics & Concepts

DecarboxylationSteric effectsCoupling (piping)Yield (engineering)MoleculeMaterials scienceChemistryChemical physicsStereochemistryCatalysisOrganic chemistryMetallurgySurface Chemistry and CatalysisMolecular Junctions and NanostructuresCovalent Organic Framework Applications