Aggregation-Induced Electrochemiluminescence of Conjugated Pdots Containing a Trace Ir(III) Complex: Insights into Structure–Property Relationships

An approach to the design of iridium(III)-contained polytetraphenylethene Pdots that could exhibit highly efficient electrochemiluminescence (ECL) was proposed. The relationships of ECL performance between the iridium complex-embedded and end-capped aggregation-induced emission (AIE) active Pdots in aqueous media were investigated for the first time. The iridium complexes with cyclometalated ligand 6-phenylphenanthridine (pphent) were incorporated into the copolymers by either embedding (P0, P2–P5) or end-capping (P1) into the backbone via an ancillary 2,2′-bipyridine (bpy) ligand. Subsequently, the corresponding Pdots of P0–P5 encapsulated with poly(styrene-co-maleicanhydride) could be obtained by the nanoprecipitation method. Compared to Pdots0, Pdots2-Pdots5 with (pphent)2Ir(bpy) (M1) complex embedding, as the iridium complex content increases, ECL signals were decreased in the order of Pdots0 > Pdots2 > Pdots3 > Pdots4 > Pdots5; whereas among these Pdots of P0–P5, Pdots1 with M1 complex end-capping exhibited the highest ECL efficiency (relative to a Ru(bpy)32+ system of 18.9%) and 4.7-fold enhancement of the ECL signal compared to the parent Pdots of P0, which was mainly attributed to the good film conductivity of the completely conjugated architectures, thus prompting the intramolecular electron transfer. This work opened new avenues for designing highly efficient ECL emitters.