Direct aryl-aryl coupling of pentacene on Au(110)

Selective C-H bond activation of polycyclic aromatic hydrocarbons is challenging due to the relatively high bond dissociation energy and the existence of multiple equivalent C-H sites. Herein, we report a scanning tunneling microscopy study on the covalent coupling of pentacene molecules on Au(110) surfaces. The missing-row reconstruction of Au(110) surfaces strengthens the molecule-substrate interactions. At elevated temperatures (470-520 K), pentacenes undergo direct aryl-aryl coupling via C-H bond activation. Due to the anisotropic feature of the reconstructed Au(110) surface, pentacenes are preferentially oriented parallel or perpendicular, making the linear and T-shaped dimers the predominant products. Based on density functional theory calculations, the aryl C-H bond activation barrier is reduced to 1.42 eV on Au(110)-(1 x 3) reconstructed surfaces, at which the extra row of gold atoms located in the (1 x 3) reconstructed grooves plays a key role.

Automated summary

This study explores the covalent coupling of pentacene molecules on Au(110) surfaces, showing that pentacenes undergo direct aryl-aryl coupling via C-H bond activation on the reconstructed Au(110) surface, forming linear and T-shaped dimers as the predominant products. The aryl C-H bond activation barrier is significantly reduced on the Au(110)-(1 x 3) reconstructed surfaces, where the extra row of gold atoms in the (1 x 3) reconstructed grooves plays a key role.