A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione

The photochemical hydrogen abstraction reaction of pyrene-4,5-dione (3) has been investigated by laser flash photolysis. Excitation (λ = 355 nm) of a degassed solution of 3 in acetonitrile resulted in the formation of a detectable transient with absorption maxima at 380 and 470 nm. This transient de...

ver descrição completa

Na minha lista:
Detalhes bibliográficos
Principais autores: Lucas, Nanci Câmara de, Elias, Mônica Maciel, Firme, Caio Lima, Corrêa, Rodrigo José, Garden, Simon John, Netto-Ferreira, José Carlos, Nicodem, David Ernest
Formato: article
Idioma:English
Publicado em: Elsevier
Assuntos:
Laser flash photolysis
Ortho-quinone
Triplet excited state
DFT
Hydrogen atom transfer
Endereço do item:https://repositorio.ufrn.br/jspui/handle/123456789/29209
Tags: Adicionar Tag
Sem tags, seja o primeiro a adicionar uma tag!
id ri-123456789-29209
record_format dspace
spelling ri-123456789-292092021-02-15T18:40:31Z A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione Lucas, Nanci Câmara de Elias, Mônica Maciel Firme, Caio Lima Corrêa, Rodrigo José Garden, Simon John Netto-Ferreira, José Carlos Nicodem, David Ernest Laser flash photolysis Ortho-quinone Triplet excited state DFT Hydrogen atom transfer The photochemical hydrogen abstraction reaction of pyrene-4,5-dione (3) has been investigated by laser flash photolysis. Excitation (λ = 355 nm) of a degassed solution of 3 in acetonitrile resulted in the formation of a detectable transient with absorption maxima at 380 and 470 nm. This transient decays with a lifetime of around 4.8 μs and is quenched by oxygen. This transient is most probably a triplet state of 3. Addition of hydrogen donors, such as 2-propanol; 1,4-cyclohexadiene or 4-methoxyphenol led to the formation of a new transient with λmax at 380, 500 nm and a broad absorption at 640 nm. This new transient slowly decays with second order kinetics and was assigned to the semiquinone radical obtained from the hydrogen abstraction reaction. Using DFT and AIM calculations the reactivity of 3 and 9,10-phenanthrenequinone (1) is best interpreted as a proton coupled electron transfer like mechanism for the hydrogen abstraction from 2-propanol. 2020-06-10T03:13:03Z 2020-06-10T03:13:03Z 2009-01-01 article LUCAS, Nanci Câmara de; ELIAS, Mônica Maciel; FIRME, Caio Lima; CORRÊA, Rodrigo José; GARDEN, Simon John; NETTO-FERREIRA, José Carlos; NICODEM, David Ernest. A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione. Journal Of Photochemistry And Photobiology A: Chemistry, [s. l.], v. 201, n. 1, p. 1-7, jan. 2009. ISSN 1010-6030. DOI https://doi.org/10.1016/j.jphotochem.2008.08.014. Disponível em: https://www.sciencedirect.com/science/article/abs/pii/S1010603008003791#!. Acesso em: 19 maio 2020. 1010-6030 https://repositorio.ufrn.br/jspui/handle/123456789/29209 10.1016/j.jphotochem.2008.08.014 en Attribution 3.0 Brazil http://creativecommons.org/licenses/by/3.0/br/ application/pdf Elsevier
institution Repositório Institucional
collection RI - UFRN
language English
topic Laser flash photolysis
Ortho-quinone
Triplet excited state
DFT
Hydrogen atom transfer
spellingShingle Laser flash photolysis
Ortho-quinone
Triplet excited state
DFT
Hydrogen atom transfer
Lucas, Nanci Câmara de
Elias, Mônica Maciel
Firme, Caio Lima
Corrêa, Rodrigo José
Garden, Simon John
Netto-Ferreira, José Carlos
Nicodem, David Ernest
A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
description The photochemical hydrogen abstraction reaction of pyrene-4,5-dione (3) has been investigated by laser flash photolysis. Excitation (λ = 355 nm) of a degassed solution of 3 in acetonitrile resulted in the formation of a detectable transient with absorption maxima at 380 and 470 nm. This transient decays with a lifetime of around 4.8 μs and is quenched by oxygen. This transient is most probably a triplet state of 3. Addition of hydrogen donors, such as 2-propanol; 1,4-cyclohexadiene or 4-methoxyphenol led to the formation of a new transient with λmax at 380, 500 nm and a broad absorption at 640 nm. This new transient slowly decays with second order kinetics and was assigned to the semiquinone radical obtained from the hydrogen abstraction reaction. Using DFT and AIM calculations the reactivity of 3 and 9,10-phenanthrenequinone (1) is best interpreted as a proton coupled electron transfer like mechanism for the hydrogen abstraction from 2-propanol.
format article
author Lucas, Nanci Câmara de
Elias, Mônica Maciel
Firme, Caio Lima
Corrêa, Rodrigo José
Garden, Simon John
Netto-Ferreira, José Carlos
Nicodem, David Ernest
author_facet Lucas, Nanci Câmara de
Elias, Mônica Maciel
Firme, Caio Lima
Corrêa, Rodrigo José
Garden, Simon John
Netto-Ferreira, José Carlos
Nicodem, David Ernest
author_sort Lucas, Nanci Câmara de
title A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
title_short A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
title_full A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
title_fullStr A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
title_full_unstemmed A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
title_sort combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
publisher Elsevier
publishDate 2020
url https://repositorio.ufrn.br/jspui/handle/123456789/29209
work_keys_str_mv AT lucasnancicamarade acombinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT eliasmonicamaciel acombinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT firmecaiolima acombinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT correarodrigojose acombinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT gardensimonjohn acombinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT nettoferreirajosecarlos acombinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT nicodemdavidernest acombinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT lucasnancicamarade combinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT eliasmonicamaciel combinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT firmecaiolima combinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT correarodrigojose combinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT gardensimonjohn combinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT nettoferreirajosecarlos combinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
AT nicodemdavidernest combinedlaserflashphotolysisdensityfunctionaltheoryandatomsinmoleculesstudyofthephotochemicalhydrogenabstractionbypyrene45dione
_version_ 1773958578933071872

Registros relacionados