Imparting Stability to Organic Photovoltaic Components through Molecular Engineering: Mitigating Reactions with Singlet Oxygen

Henke, Petr; Rindom, Cecilie; Aryal, Um Kanta; Jespersen, Malte F.; Broløs, Line; Mansø, Mads; Turkovic, Vida; Madsen, Morten; Mikkelsen, Kurt V.; Ogilby, Peter R.; Nielsen, Mogens Brøndsted

doi:10.1002/cssc.202202320

Cited by 7 publications

(2 citation statements)

References 60 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This degradation was investigated by UV–vis absorption spectroscopy; the absorption spectrum was measured over time for three different samples, and a notable change in the longest-wavelength absorption maximum was only observed for the sample that was exposed to both light and oxygen (see Figures S3 and S4 in Supporting Information File 1 ). We speculate that this degradation is due to the reaction with singlet oxygen generated by the compound as a photosensitizer; indeed, we have recently shown [ 31 ] that IF-TTF compounds are reactive towards singlet oxygen at the central fulvene bond but, in contrast, IF-TTFs (without an acetylenic moiety as in 20 ) are themselves poor photosensitizers for singlet oxygen.…”

Section: Resultsmentioning

confidence: 98%

Multi-redox indenofluorene chromophores incorporating dithiafulvene donor and ene/enediyne acceptor units

Schøttler,

Lund-Rasmussen,

Broløs

et al. 2024

Beilstein J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

Large donor–acceptor scaffolds derived from polycyclic aromatic hydrocarbons (PAHs) with tunable HOMO and LUMO energies are important for several applications, such as organic photovoltaics. Here, we present a large selection of PAHs based on central indenofluorene (IF) or fluorene cores and containing various dithiafulvene (DTF) donor units that gain aromaticity upon oxidation and a variety of acceptor units, such as vinylic diesters, enediynes, and cross-conjugated radiaannulenes (RAs) that gain aromaticity upon reduction. In some cases, the DTF units are expanded by pyrrolo annelation. The optical and redox properties of these compounds, in some cases carbon-rich, were studied by UV–vis absorption spectroscopy and cyclic voltammetry. Synthetically, the work explores IF diones or fluorenone as central building blocks by subjecting the carbonyl groups to a variety of reactions; that are, phosphite- or Lawesson’s reagent-mediated olefination reactions (to introduce DTF motifs), Ramirez/Corey–Fuchs dibromo-olefinations followed by Sonogashira couplings (to introduce enediynes motifs), and Knoevenagel condensations (to introduce the vinylic diester motif). By a subsequent Glaser–Hay coupling reaction, a RA acceptor unit was introduced to provide a DTF-IF-RA donor–acceptor scaffold with a low-energy charge-transfer absorption and multi-redox behavior.

show abstract

Section: Resultsmentioning

confidence: 98%

Multi-redox indenofluorene chromophores incorporating dithiafulvene donor and ene/enediyne acceptor units

Schøttler,

Lund-Rasmussen,

Broløs

et al. 2024

Beilstein J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Besides, imidazole could be oxidized to urea by 1 O 2 for enhanced hydrophilicity of the nanocarriers, leading to MOF disintegration. [30][31][32][33] The proposed mechanism was shown in Figure S12 (Supporting Information). The morphology and hydrodynamic size of MOF@Ce6 nanoparticles were greatly changed after being treated with laser (Figure 2b,e).…”

Section: Triple-responsive Cargo Release In Vitromentioning

confidence: 99%

Metal–Organic Framework for Hypoxia/ROS/pH Triple‐Responsive Cargo Release

Chen,

He,

Jiao

et al. 2023

Adv Healthcare Materials

View full text Add to dashboard Cite

Nanoparticulate antitumor photodynamic therapy (PDT) has been suffering from very short lifetime, limited diffusion distance of reactive oxygen species (ROS). Herein, we designed a hypoxia/ROS/pH triple‐responsive metal‐organic framework (MOF) to facilitate the on‐demand release of photosensitizers and hence enhanced PDT efficacy. Tailored azo‐containing imidazole ligand was coordinated with zinc to form MOF where photosensitizer (Chlorin e6/Ce6) was encapsulated. Azo could be reduced by overexpressed azoreductase in hypoxic tumor cells, resulting in depletion of glutathione (GSH) and thioredoxin (Trx) which are major antioxidants against ROS oxidative damage in PDT, resulting in rapid cargo release and additional efficacy amplification. The imidazole ionization caused proton sponge effect ensured the disintegration of the nanocarriers in acidic organelles, allowing the rapid release of Ce6 through lysosome escape. Under light irradiation, ROS produced by Ce6 would oxidize imidazole to urea, resulting in rapid cargo release. All of the triggers were expected to show interactive synergism. The pH‐ and hypoxia‐responsiveness could improve the release rate of Ce6 for enhanced PDT therapy, whereas the consumption of the oxygen by PDT will induce elevated hypoxia and hence in turn enhanced cargo release. This work highlights the role of triple‐responsive nanocarriers for triggered photosensitizer release and improved antitumor PDT efficacy.This article is protected by copyright. All rights reserved

show abstract

Structure–Property Relationships with Functionalized Subphthalocyanines: Toward Photovoltaic Devices More Stable to Photooxidative Degradation Mediated by Singlet Oxygen

Aryal,

Atajanov,

Broløs

et al. 2023

Adv Funct Materials

View full text Add to dashboard Cite

In this work, the overarching goal of improving the photooxidative stability of organic components used in photovoltaic devices is addressed, focusing on the common problem of degradation mediated by singlet molecular oxygen. Through a systematic exploration of boron subphthalocyanines (SubPcs), the influence of donor and acceptor substituents on the SubPc's redox properties has been examined, including the SubPc's ability to (1) act as a photosensitizer for singlet oxygen generation and (2) deactivate singlet oxygen are examined. How singlet oxygen formation and removal are influenced by linking together three SubPcs in a compact structure and by linking a SubPc to another molecular unit of relevance for organic photovoltaics (indenofluorene‐extended tetrathiafulvalene) is also examined. Synthetic protocols rooted in acetylenic scaffolding, experimental and computational structure–property relationships (optical and redox properties, singlet oxygen quantum yields, and removal kinetics), and characteristics of a functional photovoltaic device using a SubPc molecule are presented, demonstrating that cyano functionalization results in remarkably enhanced organic photovoltaic device stability.

show abstract

Imparting Stability to Organic Photovoltaic Components through Molecular Engineering: Mitigating Reactions with Singlet Oxygen

Cited by 7 publications

References 60 publications

Multi-redox indenofluorene chromophores incorporating dithiafulvene donor and ene/enediyne acceptor units

Multi-redox indenofluorene chromophores incorporating dithiafulvene donor and ene/enediyne acceptor units

Metal–Organic Framework for Hypoxia/ROS/pH Triple‐Responsive Cargo Release

Structure–Property Relationships with Functionalized Subphthalocyanines: Toward Photovoltaic Devices More Stable to Photooxidative Degradation Mediated by Singlet Oxygen

Contact Info

Product

Resources

About