Covalent Ag–C Bonding Contacts from Unprotected Terminal Acetylenes for Molecular Junctions

Robust molecule–metal linkages are essential for developing high-performance and air-stable devices for molecular and organic electronics. In this work, we report a facile method for forming robust and covalent bonding contacts between unprotected terminal acetylenes and metal (Ag) interfaces. Using this approach, we study the charge transport properties of conjugated oligophenylenes with covalent metal–carbon contacts to silver electrodes formed from unprotected terminal acetylene anchors. We performed single molecule charge transport experiments and molecular simulations on a series of arylacetylenes using gold and silver electrodes. Our results show that molecular junctions on silver electrodes spontaneously form silver–carbynyl carbon (Ag–C) contacts, resulting in a nearly 10-fold increase in conductance compared to the same molecules on gold electrodes. Overall, this work presents a simple, new electrode–anchor pair that reliably forms molecular junctions with stable and robust contacts for molecular electronics.