Dioxetane chemiluminescence. The effect of deuterium substitution on the thermal decomposition of trans-3,4-diphenyl-1,2-dioxetane

Koo, Jachoon; Schuster, Gary B.

doi:10.1021/ja00458a029

Cited by 58 publications

(19 citation statements)

References 6 publications

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“…Consequently, the bromine substituents d o not exercise any appreciable effect on the rate of decomposition of the 1,Zdioxetanes (1) that were studied here. This result is in agreement with the lack of substituent effects(Richardson et al, 1975) and the lack of kinetic isotope effects(Koo and Schuster, 1977) observed previously for 1,2-dioxetane decomposition and corroborates previous conclusions that the diradical mechanism shown in Eq. 1 operates (…”

supporting

confidence: 93%

Lack of Heavy Atom Effect on the Activation Parameters of Bromine Substituted 1,2‐dioxetanes*

Adam

Sakanishi

1979

Photochem & Photobiology

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Abstract— The continuous temperature variation kinetic method was applied to the direct chemilu‐minescence of tetramethyl‐1,2‐dioxetane (1a), 3‐bromomethyl‐3,4,4‐trimethyl‐1,2‐dioxetane (1b), 3,3–bis‐(bromomethyl‐4,4–dimethyl‐1,2–dioxetane (1c) and 3,4–bis(bromomethyl)‐3,4–dimethyl‐1,2‐dioxetane (1d). The activation energies (Ea) were found to be 27.6 ± 0.1, 28.4 ± 0.1, 28.0 ± 0.2, and 27.6 ± 0.2 kcal/mol, respectively. These results show that the heavy atom effect by the bromine substituents on the activation energies is negligible, confirming previous conclusions that a diradical mechanism operates in the thermal decomposition of these dioxetanes.

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supporting

confidence: 93%

Lack of Heavy Atom Effect on the Activation Parameters of Bromine Substituted 1,2‐dioxetanes*

Adam

Sakanishi

1979

Photochem & Photobiology

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“…) . Schuster and co‐workers have proposed a chemically initiated electron exchange luminescence (CIEEL) mechanism, first to explain the efficient chemiluminescence of diphenoyl peroxide and dimethyl‐1,2‐dioxetanone (activated by perylene), and latter to explain the efficient firefly bioluminescence . The initiating step of this mechanism is an electron transfer from an easily oxidizable electron‐rich moiety to an acceptor energy‐rich moiety (denominated as the high‐energy intermediate, HEI).…”

Section: Introductionmentioning

confidence: 99%

Mechanistic study of the unimolecular decomposition of 1,2‐dioxetanedione

Silva

2013

J of Physical Organic Chem

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The unimolecular decomposition of 1,2-dioxetanedione, the high-energy intermediate of the chemiluminescence peroxyoxalate reaction, was studied by theoretical means for the first time. Our calculations have provided results in line with the experimental data regarding this compound. 1,2-Dioxetanedione decomposes due to a step-wise biradical mechanism. In the biradical region of the decomposition path, there is a path for singlet chemiexcitation. Interactions between the singlet ground and excited states with triplet states can explain the weak unimolecular chemiluminescence of 1,2-dioxetanedione.

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“…This is also true in the case of some efficiently chemiluminescent compounds. O n the other hand, simple dioxetanes so far synthesized are fairly stable and o n thermolysis they give excited carbonyl products mainly in triplet states (Lechtken et al, 1977;Zimmerman et al, 1976;Koo and Schuster, 1977a;Umbreit and White, 1976). Quantum yields of chemiluminescence produced from them are usually very low.…”

Section: Introductionmentioning

confidence: 99%

Studies on Aminodioxetanes as a Model of Bioluminescence Intermediates. 1‐(1‐methyl‐3‐indolyl)‐6‐phenyl‐2,5,7,8‐tetraoxabicyclo[4,2,0]octane, an Aminodioxetane Resulting in Efficient Ultraviolet and Exciplex Chemiluminescence*

Nakamura

Gotot

1979

Photochem & Photobiology

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Abstract— The title aminodioxetane prepared by photooxygenation of 2–(l‐methyl‐3‐indolyl‐3‐phenyl‐1,4‐dioxene is fairly stable at −46°C and gives on warming to room temperature an ultraviolet light at Λmax 320 nm, which corresponds to 377kJ/mol; the highest energy ever observed among the efficient chemiluminescent compounds. The efficiency of chemiluminescence and excited singlet molecule formation in n‐hexane were 3.6% and at least 50%, respectively. Substitution and solvent effects suggest polar nature of the transition state as expected from the ‘CIEEL’ mechanism. In polar solvents, the dioxetane gives visible light (Λmax 400 nm in dichloromethane) as well as the UV light; the former being quenched by methanol. This is interpreted in terms of an intramolecular exciplex formation between the indole and phenyl groups. This is the first example of an intramolecular exciplex produced by the dioxetane decomposition.

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Dioxetane chemiluminescence. The effect of deuterium substitution on the thermal decomposition of trans-3,4-diphenyl-1,2-dioxetane

Cited by 58 publications

References 6 publications

Lack of Heavy Atom Effect on the Activation Parameters of Bromine Substituted 1,2‐dioxetanes*

Lack of Heavy Atom Effect on the Activation Parameters of Bromine Substituted 1,2‐dioxetanes*

Mechanistic study of the unimolecular decomposition of 1,2‐dioxetanedione

Studies on Aminodioxetanes as a Model of Bioluminescence Intermediates. 1‐(1‐methyl‐3‐indolyl)‐6‐phenyl‐2,5,7,8‐tetraoxabicyclo[4,2,0]octane, an Aminodioxetane Resulting in Efficient Ultraviolet and Exciplex Chemiluminescence*

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