Nucleic Acids With Metal‐Mediated Base Pairs and Their Applications

Metal‐mediated base pairs represent an elegant way for the site‐specific functionalisation of nucleic acids. In this type of base pair, the hydrogen bonds between complementary nucleobases are replaced formally by coordinative bonds to one or more transition‐metal ions. This Review presents an overview of metal‐mediated base pairs reported so far. It gives an insight into the characterisation of metal‐mediated base pairs and into the structures of the resulting metal‐modified nucleic acids. In addition, a summary of applications exploiting the formation of metal‐mediated base pairs is presented. The applications include, for example, metal‐ion sensors of various types, a protein sensor, and DNA‐based molecular machines. Initial reports on the potential use of metal‐mediated base pairs in the context of charge transfer through nucleic acid double helices are summarised as well.