Stationary concentration of 1O2 over 1O2 quantum yield: Next level of photoactivity analysis

Korobkov, Stepan M.; Birin, Kirill P.; Tsivadze, Aslan Yu.

doi:10.1016/j.dyepig.2023.111749

Cited by 4 publications

(3 citation statements)

References 71 publications

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“…We posit that the exceptionally high durability of I primarily stems from its structural characteristics. The main pathway of porphyrin degradation involves the addition of 1 O 2 * to CC double bonds at the meso -position of porphyrins, followed by cleavage of the C–C bonds. , This process generates a peroxide intermediate that disrupts the π-conjugated porphyrin ring and converts sp 2 -carbons into sp 3 -carbons, thereby inducing considerable distortion in the planar porphyrin structure. However, the rigid structure of I , which results from coordination of the POM and π–π interactions arising from the stacking of porphyrins, prevents the distortion of the porphyrin ring and inhibits the addition of 1 O 2 * to the meso -position of the porphyrin, thus ensuring its exceptional durability.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Consequently, the excited triplet state of porphyrins can convert molecular oxygen in its triplet state ( 3 O 2 ) to the singlet state ( 1 O 2 *), which is a reactive oxygen species with potential applications in photocatalysis and photodynamic therapy . Nevertheless, the application of porphyrins as photocatalysts and photosensitizers is often hampered by their own degradation resulting from the attack of 1 O 2 * to the meso -position of porphyrins . Therefore, there is substantial demand for the development of porphyrin-derived photocatalysts with high efficiency and durability.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, the structural rigidity of these hybrids, which stems from the coordination of POMs and the π–π stacking of porphyrins, can prevent distortion of the porphyrin rings. Given that the addition of 1 O 2 * to the meso -position of porphyrins induces the distortion of planar porphyrins, we expected that such a rigid, stacked hybrid structure would prevent the addition of 1 O 2 * and subsequent degradation. Therefore, we envisaged that porphyrin–POM hybrids with a stacked porphyrin dimer structure would demonstrate simultaneously efficient 1 O 2 * generation and high resistance to generated 1 O 2 *.…”

Section: Introductionmentioning

confidence: 99%

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Porphyrin–Polyoxotungstate Molecular Hybrid as a Highly Efficient, Durable, Visible-Light-Responsive Photocatalyst for Aerobic Oxidation Reactions

Yamaguchi,

Shioya,

et al. 2024

J. Am. Chem. Soc.

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Organic−polyoxometalate (POM) hybrids have recently attracted considerable interest because of their distinctive properties and wide-ranging applications. For the construction of organic−POM hybrids, porphyrins are promising building units owing to their optical properties and reactivity, including strong visible-light absorption and subsequent singlet-oxygen ( 1 O 2 *) generation. However, the practical utilization of porphyrins as photocatalysts and photosensitizers is often hindered by their own degradation by 1 O 2 *. Therefore, there is a substantial demand for the development of porphyrin-derived photocatalysts with both high efficiency and durability. Herein, we present a porphyrin− polyoxotungstate molecular hybrid featuring a face-to-face stacked porphyrin dimer (I) fastened by four lacunary polyoxotungstates. Hybrid I exhibited remarkable efficiency and durability in photocatalytic aerobic oxidation reactions, and the selective oxidation of various dienes, alkenes, sulfides, and amines proceeded using just 0.003 mol % of the catalyst. Mechanistic investigations suggested that the high activity of I stems from the efficient generation of 1 O 2 *, resulting from the heavy-atom effect of POMs. Furthermore, despite its high efficiency in 1 O 2 * generation compared to free porphyrins, I exhibited superior durability against 1 O 2 *-induced degradation under photoirradiation.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Porphyrin–Polyoxotungstate Molecular Hybrid as a Highly Efficient, Durable, Visible-Light-Responsive Photocatalyst for Aerobic Oxidation Reactions

Yamaguchi,

Shioya,

et al. 2024

J. Am. Chem. Soc.

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Monomeric and Dimeric Boron (III) Subphthalocyanines Functionalized with 4‐Hydroxy‐Benzoic Acid as Potential Photosensitizers and Photocatalysts in Sulfoxidation

Skvortsov,

Filatova,

Birin

et al. 2024

ChemPlusChem

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Axial modification of Boron (III) Subphthalocyanine bromide with 4‐hydroxy‐benzoic acid successfully led to the formation of macrocycle with anchored 4‐carboxyphenoxy groups [RsPcPHBA] (R= tBu, H) in the axial position and a new dimer [sPcPHBAsPc] as minor product. Tri‐tert‐butyl and unsubstituted subphthalocyanines bearing benzoate ([tBusPcBA], [sPcBA]), phenoxy‐group ([tBusPcOPh], [sPcOPh])) in the axial position, has been also investigated as control sPcs. All compounds were characterized by NMR, IR, UV‐Vis and Mass spectrometry. The electrochemical properties were studied using cyclic voltammetry (CV) and square wave voltammetry (SWV). Singlet oxygen generation was systematically measured for all synthesized [RsPcX] by kinetic method of chemical trap decomposition (DPBF) and by determination of phosphorescence of singlet oxygen species (at 1270 nm). Axially modified subphthalocyanines exhibit high quantum yields of singlet oxygen (1O2) generation (0.47‐0.62). The observed exceptional photostability in oxygen‐saturated ethanol or toluene solutions and high 1O2 quantum yields allows to use [tBusPcPHBA] as photocatalysts of selective oxidative transformations of organic sulfides to sulfoxides. Loading the catalyst to 9.7·10‐2 mol% made it possible to achieve complete conversion of the substrate (TON up to 1700).

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Phosphonate‐Substituted Pyrazinoporphyrin – a General Photocatalyst for Efficient Sulfoxidation

Polivanovskaia,

Abdulaeva,

Birin

et al. 2024

ChemPlusChem

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An exceptional efficiency of pyrazine‐annelated porphyrin as a general photocatalyst for the oxidation of organic sulfides is demonstrated. It is shown that phosphonate‐substituted pyrazinoporphyrin 2H‐1 brings together sufficient photostability and high efficiency in the aerobic photooxidation of a series of various sulfides. The influence of the reaction conditions onto the efficiency of homogeneous sulfide photooxidation in the presence of the photosensitizer (PS) was investigated and strong dependence on the solvent system was observed. The use of methanol is required for the photocatalytic sulfoxidation and the ratio of the alcohol/other solvent can significantly affect the conversion and selectivity of the reaction. The application of the prepared PS in 0.001 mol % loading allowed achieving complete conversion (97–100 %, turnover number up to 1,00,000, turnover frequency up to 6250 h−1) of substrates bearing substituents of different nature, namely aromatic and aliphatic sulfides with donor or acceptor substituents and substituents prone to oxidation, as well as cyclic sulfides. The selectivity of the of the corresponding sulfoxides formation of 96–100 % was revealed. Finally, a gram‐scale synthesis of several sulfoxides was successfully performed with the PS under investigation, providing desired products in 66–96 % yield with over 98 % purity.

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Stationary concentration of 1O2 over 1O2 quantum yield: Next level of photoactivity analysis

Cited by 4 publications

References 71 publications

Porphyrin–Polyoxotungstate Molecular Hybrid as a Highly Efficient, Durable, Visible-Light-Responsive Photocatalyst for Aerobic Oxidation Reactions

Porphyrin–Polyoxotungstate Molecular Hybrid as a Highly Efficient, Durable, Visible-Light-Responsive Photocatalyst for Aerobic Oxidation Reactions

Monomeric and Dimeric Boron (III) Subphthalocyanines Functionalized with 4‐Hydroxy‐Benzoic Acid as Potential Photosensitizers and Photocatalysts in Sulfoxidation

Phosphonate‐Substituted Pyrazinoporphyrin – a General Photocatalyst for Efficient Sulfoxidation

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