Photoinduced Electron-Transfer in 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octane

Intramolecular photoinduced electron transfer from a hydrazine unit to an aromatic group is studied by resonance Raman spectroscopy and electronic absorption spectroscopy. Substituted hydrazine functional groups have played an important role in studies of electron-transfer reactions, photoinduced in...

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Autores: Valverde Aguilar, Guadalupe, Wang, Xianghuai, Nelsen, Stephen F., Zink, Jeffrey I.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2006
País:México
Institución:Instituto Politécnico Nacional
Repositorio:Repositorio Digital del IPN
OAI Identifier:oai:www.repositoriodigital.ipn.mx:123456789/10630
Acceso en línea:http://hdl.handle.net/123456789/106
http://www.repositoriodigital.ipn.mx/handle/123456789/10630
Access Level:acceso abierto
Palabra clave:photoinduced electron transfer
resonance Raman
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spelling Photoinduced Electron-Transfer in 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octaneValverde Aguilar, GuadalupeWang, XianghuaiNelsen, Stephen F.Zink, Jeffrey I.photoinduced electron transferresonance RamanIntramolecular photoinduced electron transfer from a hydrazine unit to an aromatic group is studied by resonance Raman spectroscopy and electronic absorption spectroscopy. Substituted hydrazine functional groups have played an important role in studies of electron-transfer reactions, photoinduced intramolecular electron transfer, and of mixed valence. A prototypical compound, 2-tert-butyl-3-(anthracen-9-yl)-2,3-diazabicyclo[2.2.2]octane, that has the hydrazine-to-anthracene charge-transfer band in a region of the visible spectrum suitable for detailed resonance Raman spectroscopy is studied in detail. Excitation profiles are obtained, calculated quantitatively by using time-dependent theoretical methods, and interpreted with the assistance of molecular orbital calculations. Excited-state distortions are calculated. The largest distortions occur on the hydrazine unit; the normal mode showing the largest distortion (659 cm-1, calculated at 665 cm-1) involves an out-of-plane C-N-N-C bend consistent with removing an electron from the N-N ð antibonding orbital. Anthracene ring-centered C-C stretches also are enhanced, consistent with populating an antibonding ð orbital centered on the ring. Excellent fits to all of the excitation profiles and to the absorption band are obtained using one set of excited-state potential surfaces.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY2012-03-15T18:49:19Z2012-03-15T18:49:19Z20062013-01-16T08:36:49Z2013-01-16T08:36:49Z2013-01-16info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article0002-7863http://hdl.handle.net/123456789/106http://www.repositoriodigital.ipn.mx/handle/123456789/10630reponame:Repositorio Digital del IPNinstname:Instituto Politécnico Nacionalinstacron:IPNeninfo:eu-repo/semantics/openAccessoai:www.repositoriodigital.ipn.mx:123456789/106302026-02-18T16:40:33Z
dc.title.none.fl_str_mv Photoinduced Electron-Transfer in 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octane
title Photoinduced Electron-Transfer in 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octane
spellingShingle Photoinduced Electron-Transfer in 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octane
Valverde Aguilar, Guadalupe
photoinduced electron transfer
resonance Raman
title_short Photoinduced Electron-Transfer in 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octane
title_full Photoinduced Electron-Transfer in 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octane
title_fullStr Photoinduced Electron-Transfer in 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octane
title_full_unstemmed Photoinduced Electron-Transfer in 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octane
title_sort Photoinduced Electron-Transfer in 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octane
dc.creator.none.fl_str_mv Valverde Aguilar, Guadalupe
Wang, Xianghuai
Nelsen, Stephen F.
Zink, Jeffrey I.
author Valverde Aguilar, Guadalupe
author_facet Valverde Aguilar, Guadalupe
Wang, Xianghuai
Nelsen, Stephen F.
Zink, Jeffrey I.
author_role author
author2 Wang, Xianghuai
Nelsen, Stephen F.
Zink, Jeffrey I.
author2_role author
author
author
dc.subject.none.fl_str_mv photoinduced electron transfer
resonance Raman
topic photoinduced electron transfer
resonance Raman
description Intramolecular photoinduced electron transfer from a hydrazine unit to an aromatic group is studied by resonance Raman spectroscopy and electronic absorption spectroscopy. Substituted hydrazine functional groups have played an important role in studies of electron-transfer reactions, photoinduced intramolecular electron transfer, and of mixed valence. A prototypical compound, 2-tert-butyl-3-(anthracen-9-yl)-2,3-diazabicyclo[2.2.2]octane, that has the hydrazine-to-anthracene charge-transfer band in a region of the visible spectrum suitable for detailed resonance Raman spectroscopy is studied in detail. Excitation profiles are obtained, calculated quantitatively by using time-dependent theoretical methods, and interpreted with the assistance of molecular orbital calculations. Excited-state distortions are calculated. The largest distortions occur on the hydrazine unit; the normal mode showing the largest distortion (659 cm-1, calculated at 665 cm-1) involves an out-of-plane C-N-N-C bend consistent with removing an electron from the N-N ð antibonding orbital. Anthracene ring-centered C-C stretches also are enhanced, consistent with populating an antibonding ð orbital centered on the ring. Excellent fits to all of the excitation profiles and to the absorption band are obtained using one set of excited-state potential surfaces.
publishDate 2006
dc.date.none.fl_str_mv 2006
2012-03-15T18:49:19Z
2012-03-15T18:49:19Z
2013-01-16T08:36:49Z
2013-01-16T08:36:49Z
2013-01-16
dc.type.none.fl_str_mv info:eu-repo/semantics/publishedVersion
info:eu-repo/semantics/article
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv 0002-7863
http://hdl.handle.net/123456789/106
http://www.repositoriodigital.ipn.mx/handle/123456789/10630
identifier_str_mv 0002-7863
url http://hdl.handle.net/123456789/106
http://www.repositoriodigital.ipn.mx/handle/123456789/10630
dc.language.none.fl_str_mv en
language_invalid_str_mv en
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
publisher.none.fl_str_mv JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
dc.source.none.fl_str_mv reponame:Repositorio Digital del IPN
instname:Instituto Politécnico Nacional
instacron:IPN
instname_str Instituto Politécnico Nacional
instacron_str IPN
institution IPN
reponame_str Repositorio Digital del IPN
collection Repositorio Digital del IPN
repository.name.fl_str_mv
repository.mail.fl_str_mv
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