Elucidation of an Aggregate Excited State in the Electrochemiluminescence and Chemiluminescence of a Thermally Activated Delayed Fluorescence (TADF) Emitter

[Image: see text] The electrochemistry, electrochemiluminescence (ECL), and chemiluminescence (CL) properties of a thermally activated delayed fluorescence (TADF) emitter 4,4′-(1,2-dihydroacenaphthylene-5,6-diyl)bis(N,N-diphenylaniline) (TPA-ace-TRZ) and three of its analogues were investigated. TPA-ace-TRZ exhibits both (a) delayed onset of ECL and (b) long-persistent luminescence, which we have attributed to the formation of an aggregate excited state in excimer or exciplex form. The evidence of this aggregate excited state was consistent across ECL annihilation and coreactant pathways as well as in CL. The absolute ECL efficiency of TPA-ace-TRZ using benzoyl peroxide (BPO) as a coreactant was found to be 0.028%, which was 9-fold stronger than the [Ru(bpy)(3)](2+)/BPO reference coereactant system. Furthermore, the absolute CL quantum efficiency of TPA-ace-TRZ was determined to be 0.92%. The performance and flexibility of the TADF emitter TPA-ace-TRZ under these various emissive pathways are highly desirable toward applications in sensing, imaging, and light-emitting devices.