Luminescent Properties Variation Caused by Metal Cations Effect on the Deep Energy Levels in Cu(I) and Ag(I) Complexes

Abstract In this work, a donor‐acceptor (D‐A) type ligand is prepared to construct Cu(I) and Ag(I) complexes. These complexes possess similar molecular structures, distributions of molecular orbitals, and distributions of electrons and holes in excited states. However, they exhibit distinct photophysical properties, such as luminescent spectra and transient photo‐luminescent decay spectra. Through analysis of deep‐lying molecular orbitals in a tetrahedral field, it is determined that the variation in d‐p π conjugation between the metal cation's d‐orbitals and the π orbitals of the electron‐acceptor part of the D‐A ligand is the reason for the different photophysical properties. This research contributes to an in‐depth understanding of the role of metal ions in luminescent complexes, providing insights from the perspective of coordination chemistry.