Structural Control of Highly Efficient Thermally Activated Delayed Fluorescence in Carbene Zinc(II) Dithiolates

Luminescent metal complexes based on earth abundant elements are a valuable target to substitute 4d/5d transition metal complexes as triplet emitters in advanced photonic applications. Whereas Cu^I complexes have been thoroughly investigated in the last two decades for this purpose, no structure-property-relationships for efficient luminescence involving triplet excited states from Zn^II complexes are established. Herein, we report on the design of monomeric carbene zinc(II) dithiolates (CZT) featuring a donor-acceptor-motif that leads to highly efficient thermally activated delayed fluorescence (TADF) with for Zn^II compounds unprecedented radiative rate constants k_TADF =1.2×10⁶ s^-1 at 297 K. Our high-level DFT/MRCI calculations revealed that the relative orientation of the ligands involved in the ligand-to-ligand charge transfer (^1/3 LLCT) states is paramount to control the TADF process. Specifically, a dihedral angle of 36-40° leads to very efficient reverse intersystem-crossing (rISC) on the order of 10⁹ s^-1 due to spin-orbit coupling (SOC) mediated by the sulfur atoms in combination with a small ΔE_S1-T1 of ca. 56 meV.