Nanoparticle Linker‐Controlled Molecular Wire Devices Based on Double Molecular Monolayers

Highly conductive molecular wires are an important component for realizing molecular electronic devices and have to be explored in terms of interactions between molecules and electrodes in their molecular junctions. Here, new molecular wire junctions are reported to enhance charge transport through gold nanoparticle (AuNP)‐linked double self‐assembled monolayers (SAMs) of cobalt (II) bis‐terpyridine molecules (e.g., Co(II)(tpyphS)₂). Electrical characteristics of the double‐SAM devices are explored in terms of the existence of AuNP. The AuNP linker in the Co(II)(tpyphS)₂–AuNP–Co(II)(tpyphS)₂ junction acts as an electronic contact that is transparent to electrons. The weak temperature dependency of the AuNP‐linked molecular junctions strongly indicates sequential tunneling conduction through the highest occupied molecular orbitals (HOMOs) of Co(II)(tpyphS)₂ molecules. The electrochemical characteristics of the AuNP–Co(II)(tpyphS)₂ SAMs reveal fast electron transfer through molecules linked by AuNP. Density functional theory calculations reveal that the molecular HOMO levels are dominantly affected by the formation of junctions. The intermolecular charge transport, controlled by the AuNP linker, can provide a rational design for molecular connection that achieves a reliable electrical connectivity of molecular electronic components for construction of molecular electronic circuits.