Use of Perylene Diimides in Synthetic Photochemistry

Rosso, Cristian; Filippini, Giacomo; Prato, Maurizio

doi:10.1002/ejoc.202001616

Cited by 27 publications

(22 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Through slight alteration of these prior conditions, we were able to introduce chromophore-containing comonomers to generate materials with similar physical attributes as 1 , but with added photocatalytic capabilities. As a model, we selected the classic dye perylene diimide (PDI) as synthetically versatile redox-active moiety 28 . With the addition of 10% of PDI dibromide ( 1-C ) in the polycondensation process, we obtained a near-quantitative yield of a deep-red solid ( 1-PDI ) with high molecular weight and moderate polydispersity.…”

Section: Resultsmentioning

confidence: 99%

Solution-processable microporous polymer platform for heterogenization of diverse photoredox catalysts

et al. 2022

View full text Add to dashboard Cite

In contemporary organic synthesis, substances that access strongly oxidizing and/or reducing states upon irradiation have been exploited to facilitate powerful and unprecedented transformations. However, the implementation of light-driven reactions in large-scale processes remains uncommon, limited by the lack of general technologies for the immobilization, separation, and reuse of these diverse catalysts. Here, we report a new class of photoactive organic polymers that combine the flexibility of small-molecule dyes with the operational advantages and recyclability of solid-phase catalysts. The solubility of these polymers in select non-polar organic solvents supports their facile processing into a wide range of heterogeneous modalities. The active sites, embedded within porous microstructures, display elevated reactivity, further enhanced by the mobility of excited states and charged species within the polymers. The independent tunability of the physical and photochemical properties of these materials affords a convenient, generalizable platform for the metamorphosis of modern photoredox catalysts into active heterogeneous equivalents.

show abstract

Section: Resultsmentioning

confidence: 99%

Solution-processable microporous polymer platform for heterogenization of diverse photoredox catalysts

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Perylene diimides (PDIs) are an important class of organic dyes, which have been explored extensively in their native (charge‐neutral) forms [1] . Recently, there has been significant interest in photochemical applications of the one‐electron reduced (monoanion) forms of PDIs, whereas the two‐fold reduced (dianion) PDI species have attracted less attention [2] …”

Section: Introductionmentioning

confidence: 99%

“…[1] Recently,t here has been significant interest in photochemical applications of the oneelectron reduced (monoanion) forms of PDIs,w hereas the two-fold reduced (dianion) PDI species have attracted less attention. [2] Many fundamental studies of photoinduced electron transfer with donor-bridge-acceptor compounds incorporated PDI and related rylene diimides as electron acceptors, [3] for example to explore light-driven charge accumulation. [4] More recently,P DI monoanions attracted attention from the synthetic organic photochemistry community,t riggered by work on reductive aryl dehalogenations that were interpreted to rely on photoexcited PDIC À as the key catalytic species (Figure 1a).…”

Section: Introductionmentioning

confidence: 99%

Photophysics of Perylene Diimide Dianions and Their Application in Photoredox Catalysis

Han

Wenger

2021

Angew Chem Int Ed

View full text Add to dashboard Cite

The two-electron reduced forms of perylene diimides (PDIs) are luminescent closed-shell species whose photochemical properties seem underexplored. Our proof-of-concept study demonstrates that straightforward(single) excitation of PDI dianions with green photons provides an excited state that is similarly or more reducing than the muchshorter-lived excited states of PDI radical monoanions,w hicha re typically accessible after biphotonic excitation with blue photons. Thermodynamically demanding photocatalytic reductive dehalogenations and reductive CÀOb ond cleavage reactions of lignin model compounds have been performed using sodium dithionite acts as ar eductant, either in aqueous solution or in biphasic water-acetonitrile mixtures in the presence of aphase transfer reagent. Our work illustrates the concept of multielectron reduction of ap hotocatalyst by as acrificial reagent prior to irradiation with low-energy photons as am eans of generating very reactive excited states.

show abstract

“…This is why the bandgap in molecular crystals is comparatively small, typically in the 1.5–3.5 eV range. Photocatlytic OSNs show a marked diversity, and can be generally categorized into the following families ( Figure ): small‐molecular phthalocyanines (PCs), [ 16 ] porphyrins, [ 17 ] perylene diimides (PDIs), [ 18 ] perylene monoimides (PMIs), [ 19 ] fullerenes (C 60 , C 70 ), and polymeric graphitic carbon nitride (g‐C 3 N 4 ), [ 20 ] polypyrroles (PPYs), [ 21 ] polythiophenes (PTHs), [ 22 ] polypyridine (PPyDs), [ 23 ] polyanilines (PANIs), [ 24 ] polyimides (PIs) [ 25 ] etc. Crystalline porous polymers are an important addition to the family of polymeric photocatalysts, encompassing a broad range of systems from metal‐organic frameworks (MOFs) [ 6c ] to covalent organic frameworks (COFs).…”

Section: Revisiting the Physichemical Propertiesmentioning

confidence: 99%

Structure/Property Control in Photocatalytic Organic Semiconductor Nanocrystals

Chen

Yan

Dong

et al. 2021

Adv Funct Materials

View full text Add to dashboard Cite

Photocatalysis offers a practical solution to the ever increasing energy and environmental issues by using a semiconductor to harvest freely available sunlight. Photoactive organic semiconductor nanocrystals (OSNs) are promising photocatalysts due to their structure and function which are easily tunable by molecular design. Extensive studies have yielded significant progress on OSNs in terms of photoresponse, charge carrier mobility, as well as photoconversion efficiency. This review provides a comprehensive discussion of the emerging crystal and interface engineering strategies used in optimizing structure/property of OSNs. The basic mechanisms involved in organic photocatalysis are discussed, for a better understanding of its dependence on the molecular and supramolecular structures. Then, the intermolecular interactions in molecular packing and the kinetic and thermodynamic control over the crystal growth process are summarized, with the aim of tuning the optical and electrical properties. Band energy alignment, charge carrier dynamics, and charge transfer are discussed in different heterostructures. In each case, structure/property relationships and how to tune them are emphasized. Finally, challenges and opportunities for the practical use of the organic photocatalysts are discussed.

show abstract

Use of Perylene Diimides in Synthetic Photochemistry

Cited by 27 publications

References 65 publications

Solution-processable microporous polymer platform for heterogenization of diverse photoredox catalysts

Solution-processable microporous polymer platform for heterogenization of diverse photoredox catalysts

Photophysics of Perylene Diimide Dianions and Their Application in Photoredox Catalysis

Structure/Property Control in Photocatalytic Organic Semiconductor Nanocrystals

Contact Info

Product

Resources

About