A Metal‐Mediated Base Pair with a [2+1] Coordination Environment

A silver(I)‐mediated base pair based on azole‐derived ligands only was devised. The base pair comprises the monodentate imidazole nucleoside and a nucleoside carrying the new bidentate ligand 4‐[(1 H ‐1,2,4‐triazol‐1‐yl)methyl]‐1 H ‐1,2,3‐triazole. The silver(I) ion is hence coordinated in a trigonal planar [2+1] environment. A representative DNA duplex comprising the new base pair is stabilized by 6 °C upon binding one equivalent of silver(I). CD spectroscopy was used to confirm that the duplex adopts the canonical B‐type conformation. The base pair represents the first example of a metal‐mediated base pair with a [2+1] coordination environment.