A frontier orbital description of the reaction of singlet oxygen with simple aromatic systems

Heuvel, C. J. M. Van Den; Verhoeven, J. W.; Boer, Th. J. de

doi:10.1002/recl.19800990908

Cited by 23 publications

(16 citation statements)

References 13 publications

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“…[27,28] However, if the acene is too electron poor, no reaction with 1 O 2 occurs, nicely correlating with the HOMO energies of the aromatic systems. [26,29,30] Thus, in all experimental [22,24,31] and theoretical [29] work it has been postulated, that naphthalene (1 a) is inert towards photooxygenation. Even for 1-methyl-naphthalene (1 b) only one example of slow EPO 2 b formation was described in literature.…”

Section: Introductionmentioning

confidence: 99%

Photooxygenation of Naphthalene

Fudickar

Linker

2021

ChemPhotoChem

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The photooxygenation of naphthalene to the corresponding endoperoxide (EPO) under various conditions is described. Substantial conversion is only observed at À 10 °C and after more than two days, indicating that the [4 + 2] cycloaddition of singlet oxygen to this acene proceeds much more slowly than corresponding reactions of substituted naphthalenes, a rate constant of k = 5.4 � 0.3 M À 1 s À 1 was determined by competition kinetics. Another problem is the thermal lability and photochemical cleavage of the naphthalene EPO. We investigated the mechanism of this radical process depending on the light source and sensitizer in comparison to known cyclohexadiene EPO. Thus, bisepoxides and keto epoxides are formed after homolysis of the OÀ O bond by irradiation with sodium lamps or blue LEDs and subsequent cyclization. This process is accelerated by the sensitizers methylene blue and 9,10-dicyanoanthracene, indicating an electron transfer mechanism. Finally, the cleavage of the peroxidic bond is inhibited with red LEDs, and photooxygenation under such conditions affords 20 % EPO. Thus, we could demonstrate that contrary to literature statements singlet oxygen does indeed react with naphthalene.

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Section: Introductionmentioning

confidence: 99%

Photooxygenation of Naphthalene

Fudickar

Linker

2021

ChemPhotoChem

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“…A frontier molecular orbital (FMO) investigation of the reaction of acenes with 1 D g -O 2 was published 26 years ago. 14 However, the mechanism for addition of molecular oxygen ( 1 D g -O 2 and 3 S 2 g -O 2 ) to acenes was not studied until very recently. A recent report 13 on a theoretical study of the reaction of the acenes, benzene through pentacene, with 1 D g -O 2 prompts us to communicate our results on the two-state reactivity 15 of acenes, in particular, the reactivity of anthracene and pentacene toward 1 D g -O 2 and 3 S 2 g -O 2 .…”

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confidence: 99%

Diels–Alder reaction of acenes with singlet and triplet oxygen – theoretical study of two-state reactivity

2006

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“…The reactivity of [4 + 2] cycloadditions between anthracenes and 1 O 2 can be predicted by the frontier molecular orbital (FMO) theory, based on the energy arising from the overlap between the termini of a diene and a dienophile . The FMO theory indeed indicated a good correlation between the energy of the highest occupied molecular orbital (HOMO) of an acene as diene and the rate constant of its reaction with 1 O 2 . ,,− …”

Section: Resultsmentioning

confidence: 99%

Capture and Release of Singlet Oxygen in Coordination-Driven Self-Assembled Organoplatinum(II) Metallacycles

Fudickar

Tang

et al. 2020

J. Am. Chem. Soc.

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Singlet oxygen ( 1 O 2 ), as an important active reagent, has found wide applications in photodynamic therapy (PDT), synthetic chemistry and materials science. Organic conjugated aromatics serving as hosts to capture and release singlet oxygen have been systematically investigated over the last decades. Herein, we present a [6+6] organoplatinum(II) metallacycle by using ~180° dipyridylanthracene donor and ~120° Pt(II) acceptor as the building blocks, which enables the capture and release of singlet oxygen with relatively high photooxygenation and thermolysis rate constants. The photooxygenation of the metallacycle to the corresponding endoperoxide was performed by sensitized irradiation, and the resulting endoperoxide is stable at room temperature and can be stored under ambient condition over months. Upon simple heating the neat endoperoxide under inert atmosphere at 120 °C for 4 h, the resulting endoperoxide can be reconverted to the corresponding parent form and singlet oxygen. The photooxygenation and thermolysis products were characterized by NMR spectroscopy and ESI-TOF-MS analysis. Density functional theory calculations were conducted in order to reveal the frontier molecular orbital interactions and reactivity. This work provides a new material-platform for singlet oxygen related promising applications.

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A frontier orbital description of the reaction of singlet oxygen with simple aromatic systems

Cited by 23 publications

References 13 publications

Photooxygenation of Naphthalene

Photooxygenation of Naphthalene

Diels–Alder reaction of acenes with singlet and triplet oxygen – theoretical study of two-state reactivity

Capture and Release of Singlet Oxygen in Coordination-Driven Self-Assembled Organoplatinum(II) Metallacycles

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