Understanding the Role of NHC Ditopic Ligand Substituents in the Molecular Diversity and Emissive Properties of Silver Complexes

Abstract

Silver bis(carbene) complexes featuring ditopic N-heterocyclic carbene (NHC) ligands have been synthesized which enable the assembly of supramolecular architectures via reaction with silver triflate. Through a systematic exploration of crystal structures and emissive properties, this study investigates the impact of the substituents on the NHC ditopic ligands [R-Im-2-Z-py], where R = Me, benzyl (Bz), or 2-naphthylmethyl (NaphCH 2 ), and Z = H or Cl in the structural framework and emissive properties observed in the silver bis(carbene) or polynuclear species. Remarkably diverse structural motifs emerge in both of them, predominantly influenced by the choice of R wingtip and second by the Z substituent. Also the emissive quantum yield of the complexes is mostly governed by the selection of the R wingtip and further modulated by the Z substituent. Several of the mono and polynuclear complexes exhibit complex emissive profiles, including the observation of dual emission phenomena. Particularly noteworthy is the complex [Ag(NHC)] 2 ]OTf (R = Bz, Z = Cl), which demonstrates an exceptionally intense single blue emission with a remarkable solid-state quantum yield (Φ) of 24%.