On-Surface Synthesis by Azide–Alkyne Cycloaddition Reactions on Metal Surfaces

Arado OD, Mönig H, Fuchs H

Abstract

On-surface synthesis of covalently bond nanostructures under ultrahigh vacuum conditions has received increased attention in the recent years. This approach allows to study solvent-free chemical reactions and moreover to use well-defined substrates, which act as a catalyst and/or exerting steric effects leading to kinetic and regioselective control of the chemical process at hand. Recently, successful 1,3-dipolar azide-alkyne cycloaddition reactions were performed on metal substrates with complete regioselectivity of a specific product. This chapter presents a summary of these experimental efforts on different metal substrates, while also focusing on a comprehensive understanding of the catalyst prerequisite for on-surface coupling reactions and a quantitative description of steric effects dominating the coupling mechanism and the regioselectivity of the reaction products. Future perspectives for the bottom-up development of functional nanostructures involving on-surface azide-alkyne cycloadditions are discussed.