Dinuclear ZnII Complexes Exhibiting Thermally Activated Delayed Fluorescence and Luminescence Polymorphism

Abstract ZnII complexes exhibiting strong emission in the solid state remain scarce, and most of them exhibit only prompt fluorescence. Herein the synthesis, structures, and photoluminescence properties of two ZnII complexes containing new donor–acceptor ligands is reported. The new ZnII complexes have dinuclear structures in which each metal ion adopts a distorted square‐pyramidal geometry. The ZnII complexes show strong emission in the solid state with quantum yields up to 50 %. Variable‐temperature transient photoluminescence studies revealed an emission mechanism involving prompt and thermally activated delayed fluorescence (TADF). DFT calculations showed well‐separated HOMO and LUMO in the ground state and small excited singlet–triplet energy splitting, accounting for the TADF. The complexes also exhibit different emission colors in the as‐synthesized powder state and in single crystals, that is, they exhibit luminescence polymorphism. The single‐crystal emission is responsive to mechanical grinding and was characterized by powder XRD.