This study examines for the first time the use of an aggregation-induced emission luminogen (AIEgen, TPE_RED) as an initiator to prepare red-emitting poly(methyl methacrylate) (PMMA) polymers, i.e. PMMA_TPE_RED, for the realization of high performance luminescent solar concentrators (LSCs). TPE_RED is a photostable red-emitting AIEgen with D–A features and a 2-bromo-2-methylpropanoate unit able to initiate the ATRP polymerization of MMA. PMMA_TPE_RED polymers containing 0.98–3.05 wt% of TPE_RED absorb visible light in the range between 400 and 600 nm, and emit fluorescence at around 610–650 nm when aggregated in solution or in the solid state, with a maximum quantum yield (QY) of 26.5%. PMMA_TPE_RED films experience partial fluorescence quenching with the TPE_RED content possibly due to auto-absorption phenomena and the formation of less emissive micro-sized clusters of chromophoric entities. Physical blending of PMMA_TPE_RED with commercially available PMMA provides a film with a smooth texture and LSCs with optical efficiencies of 10% thanks to the superior light harvesting features of the homogeneously distributed AIEgen.
