AIE Polymer Films for Optical Sensing and Energy Harvesting

Pucci, Andrea

doi:10.1002/9781119643098.ch43

Cited by 3 publications

(3 citation statements)

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“…Hence, structural features of the matrix, such as morphological or conformational variations, can be identified by investigating the emissive behaviour of the AIE [ 13–15 ] making them highly promising for the development of stimuli‐responsive materials. [ 16 ]…”

Section: Introductionmentioning

confidence: 99%

“…Hence, structural features of the matrix, such as morphological or conformational variations, can be identified by investigating the emissive behaviour of the AIE [13][14][15] making them highly promising for the development of stimuli-responsive materials. [16] Tetraphenylethylene (TPE), the simplest and most common AIE, has been frequently used in combination with various polymeric matrices to endow materials with different new functionalities. In this framework, TPE has been simply blended with the polymer [17][18][19] included in microcapsules dispersed in a polymer matrix, [20,21] covalently bound to the macromolecular chains, [22] or confined into a specific ply of a multilayer structure.…”

Section: Introductionmentioning

confidence: 99%

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Emission or scattering? Discriminating the origin of responsiveness in AIEgen‐doped smart polymers using the TPE dye

et al. 2023

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Aggregation‐induced emission (AIE) luminogens are attractive dyes to probe polymer properties that depend on changes in chain mobility and free volume. When embedded in polymers the restriction of intramolecular motion (RIM) can lead to their photoluminescence quantum yield (PLQY) strong enhancement if local microviscosity increases (lowering of chain mobility and free volume). Nonetheless, measuring PLQY during stimuli, i.e. heat or mechanical stress, is technically challenging; thus, emission intensity is commonly used instead, assuming its direct correlation with the PLQY. Here, by using fluorescence lifetime as an absolute fluorescence parameter, it is demonstrated that this assumption can be invalid in many commonly encountered conditions. To this aim, different polymers are loaded with tetraphenylenethylene (TPE) and characterized during the application of thermal and mechanical stress and physical aging. Under these conditions, polymer matrix transparency variation is observed, possibly due to local changes in refractive index and to the formation of microfractures. By combining different characterization techniques, it is proved that scattering can affect the apparent emission intensity, while lifetime measurements can be used to ascertain whether the observed phenomenon is due to modifications of the photophysical properties of AIE dyes (RIM effect) or to alterations in the matrix optical properties.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Emission or scattering? Discriminating the origin of responsiveness in AIEgen‐doped smart polymers using the TPE dye

et al. 2023

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“…In addition to these computational studies, characterization of optical behavior both in solution and in a polymeric matrix was performed. A glassy polymeric surround prevents the rotational motion of fluorophore molecules, as occurs in the solid state [13]. For TPE-BPAN we chose poly(methyl methacrylate) (PMMA) as the host material, which is widely used in optical applications due to its high transparency and internal transmittance [14,15].…”

Section: Introductionmentioning

confidence: 99%

Effect of Polymer Composition on the Optical Properties of a New Aggregation-Induced Emission Fluorophore: A Combined Experimental and Computational Approach

Picchi,

Wang,

Ventura

et al. 2023

Polymers

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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.

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Effect of the Polymer Composition on the Optical Properties of a New Aggregation-Induced Emission Fluorophore: A Combined Experimental and Computational Approach

Picchi,

Wang,

Ventura

et al. 2023

Preprint

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Fluorophores with a tetraphenylethylene (TPE) core are attracting increasing interest because of their aggregation-induced emission (AIE) behaviour, which makes them particularly suitable when dispersed in thin-layer films. We propose the synthesis and use of a novel TPE fluorophore (hereafter called TPE-BPAN) decorated with two dimethylamino push groups and a 4-biphenylacetonitrile pull moiety. In tetrahydrofuran solutions, TPE-BPAN showed a broad absorption spectrum, and an intense emission is observed when a non-solvent as water is added in amounts of 70% and above. We selected and synthetized five different polymer matrices for TPE-BPAN with decreasing polarity: a) poly(methylmetacrylate) homopolymer (PMMA); b), c), and d) three copolymers of methyl methacrylate and cyclohexyl methacrylate at different compositions (P(MMA-co-CHMA) 75:25, 50:50, 25:75 mol%); e) poly(cyclohexyl methacrylate) homopolymer (PCHMA). The presence of a less polar comonomer as cyclohexyl methacrylate appeared to enhance the emission behaviour of TPE-BPAN, which displayed the highest quantum yield (QY) in P(MMA-co-CHMA) 75:25 in all the range of concentration studied from 0.4 wt.% to 2.0 wt.%. Further reduction in polarity lowered QY to the values of PMMA films; also, lower adhesion to the glass and a marked fragility of the films were observed. Referring to the P(MMA-co-CHMA) 75:25 films, QY values decreased from over 40% at 0.4 wt.% to about 30% at 2.0 wt.%, which is still helpful for energy harvesting applications such as luminescent solar concentrators (LSC). LSC performances were not significantly affected by the matrix's lower polarity and resulted in around one-third of the state-of-the-art due to the lower QY of TPE-BPAN. The theoretical investigation on density functional theory (DFT) clarified the origin of the observed AIE and the role played by the environment in modulating the photophysical behaviour.

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AIE Polymer Films for Optical Sensing and Energy Harvesting

Cited by 3 publications

References 108 publications

Emission or scattering? Discriminating the origin of responsiveness in AIEgen‐doped smart polymers using the TPE dye

Emission or scattering? Discriminating the origin of responsiveness in AIEgen‐doped smart polymers using the TPE dye

Effect of Polymer Composition on the Optical Properties of a New Aggregation-Induced Emission Fluorophore: A Combined Experimental and Computational Approach

Effect of the Polymer Composition on the Optical Properties of a New Aggregation-Induced Emission Fluorophore: A Combined Experimental and Computational Approach

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