Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe

The photophysics and photochemistry of (1-biphenyl-4-yl-1-methyl-ethyl)-tert-butyl diazene were thoroughly studied by laser flash photolysis from the picosecond to the microsecond time domain. The compound has favorable features as a radical photoinitiator and as a probe for cage effect studies in l...

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Authors: Hoijemberg, Pablo Ariel, Zerbs, Jochen, Reichardt, Christian, Schubert, Dirk W., Chesta, Carlos Alberto, Schroeder, Norberto Jorge, Aramendia, Pedro Francisco
Format: article
Status:Published version
Publication Date:2009
Country:Argentina
Institution:Consejo Nacional de Investigaciones Científicas y Técnicas
Repository:CONICET Digital (CONICET)
Language:English
OAI Identifier:oai:ri.conicet.gov.ar:11336/103300
Online Access:http://hdl.handle.net/11336/103300
Access Level:Open access
Keyword:-
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
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dc.title.none.fl_str_mv Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe
title Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe
spellingShingle Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe
Hoijemberg, Pablo Ariel
-
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
title_short Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe
title_full Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe
title_fullStr Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe
title_full_unstemmed Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe
title_sort Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe
dc.creator.none.fl_str_mv Hoijemberg, Pablo Ariel
Zerbs, Jochen
Reichardt, Christian
Schubert, Dirk W.
Chesta, Carlos Alberto
Schroeder, Norberto Jorge
Aramendia, Pedro Francisco
author Hoijemberg, Pablo Ariel
author_facet Hoijemberg, Pablo Ariel
Zerbs, Jochen
Reichardt, Christian
Schubert, Dirk W.
Chesta, Carlos Alberto
Schroeder, Norberto Jorge
Aramendia, Pedro Francisco
author_role author
author2 Zerbs, Jochen
Reichardt, Christian
Schubert, Dirk W.
Chesta, Carlos Alberto
Schroeder, Norberto Jorge
Aramendia, Pedro Francisco
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv -
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
topic -
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
description The photophysics and photochemistry of (1-biphenyl-4-yl-1-methyl-ethyl)-tert-butyl diazene were thoroughly studied by laser flash photolysis from the picosecond to the microsecond time domain. The compound has favorable features as a radical photoinitiator and as a probe for cage effect studies in liquids, supercritical fluids, and compressed gases. The biphenyl moiety acts as an antenna efficiently transferring electronic energy to the dissociative 1 n,π* state centered on the azo moiety. By picosecond experiments irradiating at the biphenyland at the azo-centered transitions, we were able to demonstrate this fact as well as determine a lifetime of 0.7 ps for the buildup of 1-biphenyl-4-yl-1-methyl-ethyl radicals (BME·). The sum of in-cage reaction rate constants of BME· radicals by combination and disproportionation is 5 × 1010 s-1 . The free radical quantum yield in solution is 0.21 (φBME·) in n-hexane at room temperature, whereas the dissociation quantum yield approaches 50%. The symmetric ketone, 2,4-bis-biphenyl-4-yl-2,4-dimethyl-pentan-2-one, was used as a reference compound for the production and reaction of BME· radicals. Transient IR measurements show CO stretching bands of the excited 3 π,π* and 1 n,π* states but no dissociation up to 0.5 ns. A fluorescence lifetime of 1 ns for this ketone is consistent with this observation. By transient actinometry and kinetic decays in the microsecond time range, we measured εBME· ) (2.3 ( 0.2) × 104 M-1 cm-1 at 325 nm and a second-order rate constant of 5.8 × 109 M-1 s-1 for the consumption of BME· radicals.
publishDate 2009
dc.date.none.fl_str_mv 2009-05
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/103300
Hoijemberg, Pablo Ariel; Zerbs, Jochen ; Reichardt, Christian ; Schubert, Dirk W.; Chesta, Carlos Alberto; et al.; Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe; American Chemical Society; Journal of Physical Chemistry A; 113; 19; 5-2009; 5531-5539
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/103300
identifier_str_mv Hoijemberg, Pablo Ariel; Zerbs, Jochen ; Reichardt, Christian ; Schubert, Dirk W.; Chesta, Carlos Alberto; et al.; Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe; American Chemical Society; Journal of Physical Chemistry A; 113; 19; 5-2009; 5531-5539
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/full/10.1021/jp809315u
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp809315u
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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spelling Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect ProbeHoijemberg, Pablo ArielZerbs, JochenReichardt, ChristianSchubert, Dirk W.Chesta, Carlos AlbertoSchroeder, Norberto JorgeAramendia, Pedro Francisco-https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The photophysics and photochemistry of (1-biphenyl-4-yl-1-methyl-ethyl)-tert-butyl diazene were thoroughly studied by laser flash photolysis from the picosecond to the microsecond time domain. The compound has favorable features as a radical photoinitiator and as a probe for cage effect studies in liquids, supercritical fluids, and compressed gases. The biphenyl moiety acts as an antenna efficiently transferring electronic energy to the dissociative 1 n,π* state centered on the azo moiety. By picosecond experiments irradiating at the biphenyland at the azo-centered transitions, we were able to demonstrate this fact as well as determine a lifetime of 0.7 ps for the buildup of 1-biphenyl-4-yl-1-methyl-ethyl radicals (BME·). The sum of in-cage reaction rate constants of BME· radicals by combination and disproportionation is 5 × 1010 s-1 . The free radical quantum yield in solution is 0.21 (φBME·) in n-hexane at room temperature, whereas the dissociation quantum yield approaches 50%. The symmetric ketone, 2,4-bis-biphenyl-4-yl-2,4-dimethyl-pentan-2-one, was used as a reference compound for the production and reaction of BME· radicals. Transient IR measurements show CO stretching bands of the excited 3 π,π* and 1 n,π* states but no dissociation up to 0.5 ns. A fluorescence lifetime of 1 ns for this ketone is consistent with this observation. By transient actinometry and kinetic decays in the microsecond time range, we measured εBME· ) (2.3 ( 0.2) × 104 M-1 cm-1 at 325 nm and a second-order rate constant of 5.8 × 109 M-1 s-1 for the consumption of BME· radicals.Fil: Hoijemberg, Pablo Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Zerbs, Jochen. Georg August Universitat; AlemaniaFil: Reichardt, Christian. Max planck institute of Biophysical Chemistry; AlemaniaFil: Schubert, Dirk W.. Max planck institute of Biophysical Chemistry; AlemaniaFil: Chesta, Carlos Alberto. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Schroeder, Norberto Jorge. Georg August Universitat; AlemaniaFil: Aramendia, Pedro Francisco. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaAmerican Chemical Society2009-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/103300Hoijemberg, Pablo Ariel; Zerbs, Jochen ; Reichardt, Christian ; Schubert, Dirk W.; Chesta, Carlos Alberto; et al.; Photophysics and Photochemistry of an Asymmetrically Substituted Diazene: A Suitable Cage Effect Probe; American Chemical Society; Journal of Physical Chemistry A; 113; 19; 5-2009; 5531-55391089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/full/10.1021/jp809315uinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp809315uinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2024-05-08T13:52:56Zoai:ri.conicet.gov.ar:11336/103300instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982024-05-08 13:52:57.231CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
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