A nine-ring fused terrylene diimide exhibits switching between red TADF and near-IR room temperature phosphorescence

Herein, we report the first example of a terrylene diimide derivative that switches emission between thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) in the red region. By design, the molecule TDI-cDBT boasts a symmetrical, consecutively fused nine-ring motif with a kite-like structure. The rigid core formed by the annulated dibenzothiophene moiety favoured efficient intersystem crossing and yielded a narrow-band emission with a full-width half maxima (FWHM) of 0.09 eV, along with high colour purity. A small ΔE _S of 0.04 eV facilitated thermally activated delayed fluorescence, enhancing the quantum yield to 88% in the red region. Additionally, it also prefers a direct triplet emission from the aggregated state. The room temperature phosphorescence observed from the aggregates has a longer emission lifetime of 1.8 ms, which is further prolonged to 8 ms at 77 K in the NIR region. Thus, the current strategy is successful in not only reducing ΔE _S to favour TADF but also serves as a novel platform that can switch emission from TADF to RTP depending upon the concentration.