INFLUÊNCIA DA RIGIDEZ DO MEIO NA CINÉTICA DO FOTOCROMISMO DE DITIZONATOS METÁLICOS

Detalhes bibliográficos
Autor(a) principal: Barros,Cristiane Lázara de
Data de Publicação: 2018
Outros Autores: Barbosa Neto,Newton Martins, Patrocinio,Antonio Otavio T.
Tipo de documento: Artigo
Idioma: por
Título da fonte: Química Nova (Online)
Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000900999
Resumo: The kinetics of photoisomerization and thermal back reaction of mercury(II) and zinc(II) dithizonates, M(HDz)2, were analyzed by photolysis assays in fluid solution and in poly(methyl methacrylate), PMMA, films. In fluid solution, the photo- and thermoisomerization of both complexes can be described by a single exponential function. The Zn(II) dithizonate exhibits rate constants three orders of magnitude greater than that for Hg(II) complex, which is attributed to the higher charge density of the Zn(II) cation. In PMMA films, the thermal back reaction of both complexes can only be described by bi-exponential functions. On this more rigid medium the rate constants are about one order of magnitude slower than the respective ones in fluid solution and the bi-exponential behavior is related to regions in the polymeric matrix with distinct free volumes. The rate constants for both photo- and thermoisomerization of Zn(HDz)2 in PMMA are reported for the first time and are compared with the well-studied Hg(II) analog. The experimental data provides insights on the role of the metal cation on the photocromic behavior in rigid media, which can lately contribute for technological applications.
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spelling INFLUÊNCIA DA RIGIDEZ DO MEIO NA CINÉTICA DO FOTOCROMISMO DE DITIZONATOS METÁLICOSphotochromismmetal dithizonatesphotoisomerizationThe kinetics of photoisomerization and thermal back reaction of mercury(II) and zinc(II) dithizonates, M(HDz)2, were analyzed by photolysis assays in fluid solution and in poly(methyl methacrylate), PMMA, films. In fluid solution, the photo- and thermoisomerization of both complexes can be described by a single exponential function. The Zn(II) dithizonate exhibits rate constants three orders of magnitude greater than that for Hg(II) complex, which is attributed to the higher charge density of the Zn(II) cation. In PMMA films, the thermal back reaction of both complexes can only be described by bi-exponential functions. On this more rigid medium the rate constants are about one order of magnitude slower than the respective ones in fluid solution and the bi-exponential behavior is related to regions in the polymeric matrix with distinct free volumes. The rate constants for both photo- and thermoisomerization of Zn(HDz)2 in PMMA are reported for the first time and are compared with the well-studied Hg(II) analog. The experimental data provides insights on the role of the metal cation on the photocromic behavior in rigid media, which can lately contribute for technological applications.Sociedade Brasileira de Química2018-09-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000900999Química Nova v.41 n.9 2018reponame:Química Nova (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.21577/0100-4042.20170280info:eu-repo/semantics/openAccessBarros,Cristiane Lázara deBarbosa Neto,Newton MartinsPatrocinio,Antonio Otavio T.por2018-10-11T00:00:00Zoai:scielo:S0100-40422018000900999Revistahttps://www.scielo.br/j/qn/ONGhttps://old.scielo.br/oai/scielo-oai.phpquimicanova@sbq.org.br1678-70640100-4042opendoar:2018-10-11T00:00Química Nova (Online) - Sociedade Brasileira de Química (SBQ)false
dc.title.none.fl_str_mv INFLUÊNCIA DA RIGIDEZ DO MEIO NA CINÉTICA DO FOTOCROMISMO DE DITIZONATOS METÁLICOS
title INFLUÊNCIA DA RIGIDEZ DO MEIO NA CINÉTICA DO FOTOCROMISMO DE DITIZONATOS METÁLICOS
spellingShingle INFLUÊNCIA DA RIGIDEZ DO MEIO NA CINÉTICA DO FOTOCROMISMO DE DITIZONATOS METÁLICOS
Barros,Cristiane Lázara de
photochromism
metal dithizonates
photoisomerization
title_short INFLUÊNCIA DA RIGIDEZ DO MEIO NA CINÉTICA DO FOTOCROMISMO DE DITIZONATOS METÁLICOS
title_full INFLUÊNCIA DA RIGIDEZ DO MEIO NA CINÉTICA DO FOTOCROMISMO DE DITIZONATOS METÁLICOS
title_fullStr INFLUÊNCIA DA RIGIDEZ DO MEIO NA CINÉTICA DO FOTOCROMISMO DE DITIZONATOS METÁLICOS
title_full_unstemmed INFLUÊNCIA DA RIGIDEZ DO MEIO NA CINÉTICA DO FOTOCROMISMO DE DITIZONATOS METÁLICOS
title_sort INFLUÊNCIA DA RIGIDEZ DO MEIO NA CINÉTICA DO FOTOCROMISMO DE DITIZONATOS METÁLICOS
author Barros,Cristiane Lázara de
author_facet Barros,Cristiane Lázara de
Barbosa Neto,Newton Martins
Patrocinio,Antonio Otavio T.
author_role author
author2 Barbosa Neto,Newton Martins
Patrocinio,Antonio Otavio T.
author2_role author
author
dc.contributor.author.fl_str_mv Barros,Cristiane Lázara de
Barbosa Neto,Newton Martins
Patrocinio,Antonio Otavio T.
dc.subject.por.fl_str_mv photochromism
metal dithizonates
photoisomerization
topic photochromism
metal dithizonates
photoisomerization
description The kinetics of photoisomerization and thermal back reaction of mercury(II) and zinc(II) dithizonates, M(HDz)2, were analyzed by photolysis assays in fluid solution and in poly(methyl methacrylate), PMMA, films. In fluid solution, the photo- and thermoisomerization of both complexes can be described by a single exponential function. The Zn(II) dithizonate exhibits rate constants three orders of magnitude greater than that for Hg(II) complex, which is attributed to the higher charge density of the Zn(II) cation. In PMMA films, the thermal back reaction of both complexes can only be described by bi-exponential functions. On this more rigid medium the rate constants are about one order of magnitude slower than the respective ones in fluid solution and the bi-exponential behavior is related to regions in the polymeric matrix with distinct free volumes. The rate constants for both photo- and thermoisomerization of Zn(HDz)2 in PMMA are reported for the first time and are compared with the well-studied Hg(II) analog. The experimental data provides insights on the role of the metal cation on the photocromic behavior in rigid media, which can lately contribute for technological applications.
publishDate 2018
dc.date.none.fl_str_mv 2018-09-01
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000900999
url http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0100-40422018000900999
dc.language.iso.fl_str_mv por
language por
dc.relation.none.fl_str_mv 10.21577/0100-4042.20170280
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv text/html
dc.publisher.none.fl_str_mv Sociedade Brasileira de Química
publisher.none.fl_str_mv Sociedade Brasileira de Química
dc.source.none.fl_str_mv Química Nova v.41 n.9 2018
reponame:Química Nova (Online)
instname:Sociedade Brasileira de Química (SBQ)
instacron:SBQ
instname_str Sociedade Brasileira de Química (SBQ)
instacron_str SBQ
institution SBQ
reponame_str Química Nova (Online)
collection Química Nova (Online)
repository.name.fl_str_mv Química Nova (Online) - Sociedade Brasileira de Química (SBQ)
repository.mail.fl_str_mv quimicanova@sbq.org.br
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