Efficient Reverse Intersystem Crossing in Carbene‐Copper‐Amide TADF Emitters via an Intermediate Triplet State

Abstract

AbstractThe mechanism behind reverse intersystem crossing (rISC) in metal‐based TADF emitters is still under debate. Thermal rISC necessitates small singlet/triplet energy gaps as realized in donor‐acceptor systems with charge‐transfer excited states. However, their associated spin‐orbit couplings are too small to account for effective rISC. Here, we report the first nonadiabatic dynamics simulation of the rISC process in a carbene‐copper(I)‐carbazolyl TADF emitter. Efficient rISC on a picosecond time scale is demonstrated for an initial triplet minimum geometry that exhibits a perpendicular orientation of the ligands. The dynamics involves an intermediate higher‐lying triplet state of metal‐to‐ligand charge transfer character (3MLCT), which enables large spin‐orbit couplings with the lowest singlet charge transfer state. The mechanism is completed in the S1state, where the complex can return to a co‐planar coordination geometry that presents high fluorescence efficiency.