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

Author:

Mitra Mousree1,Mrózek Ondřej1,Putscher Markus2,Guhl Jasper2ORCID,Hupp Benjamin1ORCID,Belyaev Andrey1,Marian Christel M.2ORCID,Steffen Andreas1ORCID

Affiliation:

1. Faculty of Chemistry and Chemical Biology TU Dortmund University Otto-Hahn-Str. 6 44227 Dortmund Germany

2. Institute of Theoretical and Computational Chemistry Faculty of Mathematics and Natural Sciences Heinrich Heine University Düsseldorf Universitätsstr. 1 40225 Düsseldorf Germany

Abstract

AbstractLuminescent 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 CuI 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 ZnII 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 ZnII compounds unprecedented radiative rate constants kTADF=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 (1/3LLCT) 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 ΔES1‐T1 of ca. 56 meV.

Funder

Deutsche Forschungsgemeinschaft

Alexander von Humboldt-Stiftung

Publisher

Wiley

Subject

General Chemistry,Catalysis

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