On-surface polyarylene synthesis by cycloaromatization of isopropyl substituents

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