Tailoring Carbene-Metal-Amides for Thermally Activated Delayed Fluorescence: A Computationally Guided Study on the...

Gold-centered carbene-metal-amides (CMAs) containing cyclic (alkyl)(amino)carbenes (CAACs) are promising emitters for thermally activated delayed fluorescence (TADF). Aiming at the design and optimization of new TADF emitters, we report a density functional theory study of over 60 CMAs with various CAAC ligands, systematically evaluating computed parameters in relation to photoluminescence properties. The CMA structures were primarily selected based on experimental synthesis prospects. We demonstrate that TADF efficiency of the CMA materials originates from a compromise between oscillator strength coefficients and exchange energy (ΔE_ST). The latter is governed by the overlap of HOMO and LUMO orbitals, where HOMO is localized on the amide and LUMO over the Au-carbene bond. The S₀ ground and excited T₁ states of the CMAs adopt approximately coplanar geometry of carbene and amide ligands, but rotate perpendicular in the excited S₁ states, resulting in degeneracy or near-degeneracy of S₁ and T₁, accompanied by a decrease in the S₁-S₀ oscillator strength from its maximum at coplanar geometries to near zero at rotated geometries. Based on the computations, promising new TADF emitters are proposed and synthesized. Bright CMA complex (^Et2CAAC)Au(carbazolide) is obtained and fully characterized in order to demonstrate that excellent stability and high radiative rates up to 10⁶ s^-1 can be obtained for the gold-CMA complexes with small CAAC-carbene ligands.