Tandem Desulfurization/C-C Coupling Reaction of Tetrathienylbenzenes on Cu(111): Synthesis of Pentacene and an Exotic Ladder Polymer

Surface-confined reactions represent a powerful approach for the precise synthesis of low-dimensional organic materials. A complete understanding of the pathways of surface reactions would enable the rational synthesis of a wide range of molecules and polymers. Here, we report different reaction pathways of tetrathienylbenzene (T1TB) and its extended congener tetrakis(dithienyl)benzene (T2TB) on Cu(111), investigated using scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. Both T1TB and T2TB undergo desulfurization when deposited on Cu(111) at room temperature. Deposition of T1TB at 453 K yields pentacene through desulfurization, hydrogen transfer, and a cascade of intramolecular cyclization. In contrast, for T2TB the intramolecular cyclization stops at anthracene and the following intermolecular C-C coupling produces a conjugated ladder polymer. We show that tandem desulfurization/C-C coupling provides a versatile approach for growing carbon-based nanostructures on metal surfaces.

Automated summary

Surface-confined reactions are a powerful method for synthesizing low-dimensional organic materials. Understanding the reaction pathways can enable the rational synthesis of various molecules and polymers. In this study, different reaction pathways of tetrathienylbenzene and its extended congener on Cu(111) were investigated using scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations.