Finding Design Principles of OLED Emitters through Theoretical Investigations of Zn(II) Carbene Complexes

In this work, Zn(II) carbene complexes carrying a dianionic 1,2-dithiolbenzene (dtb) or 1,2-diolbenzene (dob) ligand were investigated regarding their suitability as organic light-emitting diode (OLED) emitter. For the optimization of the complexes, density functional-based methods were used and frequency analyses verified the obtained structures as minima. All calculations were carried out including a polarizable continuum model to mimic solvent-solute interactions. Multireference configuration interaction methods were used to determine excitation energies, spin-orbit couplings, and luminescence properties. Rate constants of spin-allowed and spin-forbidden transitions were calculated according to a Fermi golden rule expression. Using carbene ligands with varying σ-donor and π-acceptor strengths, the luminescence is found to be tunable from yellow to orange/red to deep red/near-infrared. The calculated intersystem crossing (ISC) time constants indicate thermally activated delayed fluorescence (TADF) to be the main decay channel. In contrast to many d¹⁰ coinage metal complexes, a parallel orientation of dtb or dob and the carbene ligand is found to be highly favorable. For the complexes with a cyclic (alkyl)(amino) carbene (CAAC) or cyclic (amino)(aryl) carbene (CAArC) ligand, the S₁ and T₁ states have ligand-to-ligand charge-transfer (LLCT) character and are energetically close. The complex with a classical N-heterocyclic carbene (NHC) ligand has S₁ and T₁ states with mixed ligand-to-metal charge-transfer (LMCT)/LLCT character and is a very rare example in which the zinc ion contributes to the excitation.