On-surface polyarylene synthesis by cycloaromatization of isopropyl substituents

Abstract

Immobilization of organic molecules on metal surfaces and their coupling via thermally induced C–C bond formation is an important technique in organic and polymer synthesis. Using this approach, insoluble and reactive carbon nanostructures can be synthesized and the reactions monitored in situ using scanning probe microscopy methods. The diversity of conceivable products, however, is limited by the number and variety of known on-surface reactions. Here, we introduce the on-surface synthesis of polyarylenes by intermolecular oxidative coupling of isopropyl substituents of arenes. This [3+3] dimerization reaction forms a new phenylene ring and can be regarded as a formal cycloaromatization. The synthetic value of this reaction is proved by the synthesis of polyarylenes and co-polyarylenes, which we demonstrate by synthesizing poly(2,7-pyrenylene-1,4-phenylene). Scanning tunnelling microscopy and non-contact atomic force microscopy studies, complemented by density functional theory calculations, offer mechanistic insight into the on-surface cycloaromatization reaction. On-surface methods can be used to synthesize organic molecules, polymers and nanomaterials, however, the diversity of conceivable products is limited by the number of known on-surface reactions. Now, a phenylene ring-forming reaction on a gold surface by intermolecular oxidative coupling of isopropyl substituents on arenes is reported. The reaction is probed using bond-resolved imaging and computational modelling.