Understanding the luminescence properties of Cu(i) complexes: a quantum chemical perusal

Electronic structures and excited-state properties of Cu(i) complexes with varying coordination numbers have been investigated by means of advanced quantum chemical methods. The computational protocol employs density functional-based methods for geometry optimizations and vibrational analyses including solvent effects through continuum models. Excitation energies, spin-orbit couplings and luminescence properties are evaluated using multireference configuration interaction methods. Rate constants of spin-allowed and spin-forbidden transitions have been determined according to the Fermi golden rule. The computational results for the 4-coordinate (DPEPhos)Cu(PyrTet), the 3-coordinate [IPr-Cu-Py-2](+), and the linear CAAC(2)(Me)-Cu-Cl complexes agree well with experimental absorption and emission wavelengths, intersystem crossing (ISC) time constants, and radiative lifetimes in liquid solution. Spectral shifts on the ligand-to-ligand charge transfer (LLCT) and metal-to-ligand charge transfer (MLCT) transitions caused by the polarity of the environment are well represented by the continuum models whereas the shifts caused by pseudo-Jahn-Teller distortions in the MLCT states are too pronounced in comparison to solid-state data. Systematic variation of the ligands in linear Cu(i) carbene complexes shows that only those complexes with S-1 and T-1 states of LLCT character possess sufficiently small singlet-triplet energy gaps Delta E-ST to enable thermally activated delayed fluorescence (TADF). Complexes whose S-1 and T-1 wavefunctions are dominated by MLCT excitations tend to emit phosphorescence instead. Unlike the situation in metal-free TADF emitters, the presence of low-lying locally excited triplet states does not promote ISC. These states rather hold the danger of trapping the excitation with nonradiative deactivation being the major deactivation channel.