ABSTRACT
Nowadays, fluorophores with a tetraphenylethylene (TPE) core are considered interesting due to the aggregation-induced emission (AIE) behavior that enables their effective use in polymer films. We propose a novel TPE fluorophore (TPE-BPAN) bearing two dimethylamino push and a 4-biphenylacetonitrile pull moieties with the typical AIE characteristics in solution and in the solid state, as rationalized by DFT calculations. Five different host polymer matrices with different polarity have been selected: two homopolymers of poly(methylmethacrylate) (PMMA) and poly(cyclohexyl methacrylate) (PCHMA) and three copolymers at different compositions (P(MMA-co-CHMA) 75:25, 50:50, and 25:75 mol%). The less polar comonomer of CHMA appeared to enhance TPE-BPAN emission with the highest quantum yield (QY) of about 40% measured in P(MMA-co-CHMA) 75:25. Further reduction in polymer polarity lowered QY and decreased the film stability and adhesion to the glass surface. LSC performances were not significantly affected by the matrix's polarity and resulted in around one-third of the state-of-the-art due to the reduced QY of TPE-BPAN. The theoretical investigation based on density functional theory (DFT) calculations clarified the origin of the observed AIE and the role played by the environment in modulating the photophysical behavior.
ABSTRACT
Luminescent solar concentrators (LSCs) are a class of optical devices able to harvest, downshift, and concentrate sunlight, thanks to the presence of emitting materials embedded in a polymer matrix. Use of LSCs in combination with silicon-based photovoltaic (PV) devices has been proposed as a viable strategy to enhance their ability to harvest diffuse light and facilitate their integration in the built environment. LSC performances can be improved by employing organic fluorophores with strong light absorption in the center of the solar spectrum and intense, red-shifted emission. In this work, we present the design, synthesis, characterization, and application in LSCs of a series of orange/red organic emitters featuring a benzo[1,2-b:4,5-b']dithiophene 1,1,5,5-tetraoxide central core as an acceptor (A) unit. The latter was connected to different donor (D) and acceptor (A') moieties by means of Pd-catalyzed direct arylation reactions, yielding compounds with either symmetric (D-A-D) or non-symmetric (D-A-A') structures. We found that upon light absorption, the compounds attained excited states with a strong intramolecular charge-transfer character, whose evolution was greatly influenced by the nature of the substituents. In general, symmetric structures showed better photophysical properties for the application in LSCs than their non-symmetric counterparts, and using a donor group of moderate strength such as triphenylamine was found preferable. The best LSC built with these compounds presented photonic (external quantum efficiency of 8.4 ± 0.1%) and PV (device efficiency of 0.94 ± 0.06%) performances close to the state-of-the-art, coupled with a sufficient stability in accelerated aging tests.
