Manganese(ii) Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Outros Autores: | , , , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1039/d1nj00493j http://hdl.handle.net/11449/206465 |
Resumo: | A series of new manganese(ii) complexes were prepared with three bidentate Schiff-base ligands derived by condensation of salicylaldehyde and different cycloalkylamines (cycloalkyl = cyclopentyl, cyclohexyl, and cycloheptyl): [Mn(CyPen-Salicyl)2] (1), [Mn(CyHex-Salicyl)2] (2), and [Mn(CyHep-Salicyl)2] (3). The complexes 1-3 were characterized by FTIR, UV-vis and EPR spectroscopy, elemental analysis, cyclic voltammetry, and computational methods. The manganese(ii) complexes (1-3) were used as controlling agents for the polymerization of vinyl acetate (VAc) initiated by AIBN according to an organometallic-mediated radical polymerization (OMRP) mechanism. The VAc polymerization mediated by the Mn complexes suggests that the control level can be slightly tuned through substitution of the cycloalkyl group on the Schiff-base ligand. Kinetics studies and computational investigations support an RT mechanism and a tailorable Mn complex reactivity mainly altered by steric factors of the Schiff-base ligands. The calculated thermodynamic parameters agree with the mediating ability of these complexes, since the degree of polymerization control decreases with increasing steric hindrance of the Schiff-base ligands, as well as with increasing ΔG values for the formation of dormant species. |
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Repositório Institucional da UNESP |
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spelling |
Manganese(ii) Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetateA series of new manganese(ii) complexes were prepared with three bidentate Schiff-base ligands derived by condensation of salicylaldehyde and different cycloalkylamines (cycloalkyl = cyclopentyl, cyclohexyl, and cycloheptyl): [Mn(CyPen-Salicyl)2] (1), [Mn(CyHex-Salicyl)2] (2), and [Mn(CyHep-Salicyl)2] (3). The complexes 1-3 were characterized by FTIR, UV-vis and EPR spectroscopy, elemental analysis, cyclic voltammetry, and computational methods. The manganese(ii) complexes (1-3) were used as controlling agents for the polymerization of vinyl acetate (VAc) initiated by AIBN according to an organometallic-mediated radical polymerization (OMRP) mechanism. The VAc polymerization mediated by the Mn complexes suggests that the control level can be slightly tuned through substitution of the cycloalkyl group on the Schiff-base ligand. Kinetics studies and computational investigations support an RT mechanism and a tailorable Mn complex reactivity mainly altered by steric factors of the Schiff-base ligands. The calculated thermodynamic parameters agree with the mediating ability of these complexes, since the degree of polymerization control decreases with increasing steric hindrance of the Schiff-base ligands, as well as with increasing ΔG values for the formation of dormant species.Faculdade de Ciências e Tecnologia UNESP-Univ. Estadual PaulistaInstituto de Química Universidade Federal de Uberlândia, P.O. Box 593CEITEC-Central European Institute of Technology Brno University of Technology, Purkyňova 123Instituto de Física de São Carlos Usp Universidade de São PauloFaculdade de Ciências e Tecnologia UNESP-Univ. Estadual PaulistaUniversidade Estadual Paulista (Unesp)Universidade Federal de Uberlândia (UFU)Brno University of TechnologyUniversidade de São Paulo (USP)Hashimoto, Patricia K. [UNESP]Oliveira, Larissa F. [UNESP]Riga-Rocha, Beatriz A. [UNESP]MacHado, Antonio E. H.Santana, Vinicius T.Nascimento, Otaciro R.Carvalho-Jr, Valdemiro P. [UNESP]Goi, Beatriz E. [UNESP]2021-06-25T10:32:26Z2021-06-25T10:32:26Z2021-06-14info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article10109-10117http://dx.doi.org/10.1039/d1nj00493jNew Journal of Chemistry, v. 45, n. 22, p. 10109-10117, 2021.1369-92611144-0546http://hdl.handle.net/11449/20646510.1039/d1nj00493j2-s2.0-85107708263Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengNew Journal of Chemistryinfo:eu-repo/semantics/openAccess2021-10-23T05:25:45Zoai:repositorio.unesp.br:11449/206465Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T21:23:24.968073Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Manganese(ii) Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate |
title |
Manganese(ii) Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate |
spellingShingle |
Manganese(ii) Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate Hashimoto, Patricia K. [UNESP] |
title_short |
Manganese(ii) Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate |
title_full |
Manganese(ii) Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate |
title_fullStr |
Manganese(ii) Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate |
title_full_unstemmed |
Manganese(ii) Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate |
title_sort |
Manganese(ii) Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate |
author |
Hashimoto, Patricia K. [UNESP] |
author_facet |
Hashimoto, Patricia K. [UNESP] Oliveira, Larissa F. [UNESP] Riga-Rocha, Beatriz A. [UNESP] MacHado, Antonio E. H. Santana, Vinicius T. Nascimento, Otaciro R. Carvalho-Jr, Valdemiro P. [UNESP] Goi, Beatriz E. [UNESP] |
author_role |
author |
author2 |
Oliveira, Larissa F. [UNESP] Riga-Rocha, Beatriz A. [UNESP] MacHado, Antonio E. H. Santana, Vinicius T. Nascimento, Otaciro R. Carvalho-Jr, Valdemiro P. [UNESP] Goi, Beatriz E. [UNESP] |
author2_role |
author author author author author author author |
dc.contributor.none.fl_str_mv |
Universidade Estadual Paulista (Unesp) Universidade Federal de Uberlândia (UFU) Brno University of Technology Universidade de São Paulo (USP) |
dc.contributor.author.fl_str_mv |
Hashimoto, Patricia K. [UNESP] Oliveira, Larissa F. [UNESP] Riga-Rocha, Beatriz A. [UNESP] MacHado, Antonio E. H. Santana, Vinicius T. Nascimento, Otaciro R. Carvalho-Jr, Valdemiro P. [UNESP] Goi, Beatriz E. [UNESP] |
description |
A series of new manganese(ii) complexes were prepared with three bidentate Schiff-base ligands derived by condensation of salicylaldehyde and different cycloalkylamines (cycloalkyl = cyclopentyl, cyclohexyl, and cycloheptyl): [Mn(CyPen-Salicyl)2] (1), [Mn(CyHex-Salicyl)2] (2), and [Mn(CyHep-Salicyl)2] (3). The complexes 1-3 were characterized by FTIR, UV-vis and EPR spectroscopy, elemental analysis, cyclic voltammetry, and computational methods. The manganese(ii) complexes (1-3) were used as controlling agents for the polymerization of vinyl acetate (VAc) initiated by AIBN according to an organometallic-mediated radical polymerization (OMRP) mechanism. The VAc polymerization mediated by the Mn complexes suggests that the control level can be slightly tuned through substitution of the cycloalkyl group on the Schiff-base ligand. Kinetics studies and computational investigations support an RT mechanism and a tailorable Mn complex reactivity mainly altered by steric factors of the Schiff-base ligands. The calculated thermodynamic parameters agree with the mediating ability of these complexes, since the degree of polymerization control decreases with increasing steric hindrance of the Schiff-base ligands, as well as with increasing ΔG values for the formation of dormant species. |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-06-25T10:32:26Z 2021-06-25T10:32:26Z 2021-06-14 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://dx.doi.org/10.1039/d1nj00493j New Journal of Chemistry, v. 45, n. 22, p. 10109-10117, 2021. 1369-9261 1144-0546 http://hdl.handle.net/11449/206465 10.1039/d1nj00493j 2-s2.0-85107708263 |
url |
http://dx.doi.org/10.1039/d1nj00493j http://hdl.handle.net/11449/206465 |
identifier_str_mv |
New Journal of Chemistry, v. 45, n. 22, p. 10109-10117, 2021. 1369-9261 1144-0546 10.1039/d1nj00493j 2-s2.0-85107708263 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
New Journal of Chemistry |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
10109-10117 |
dc.source.none.fl_str_mv |
Scopus reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
instname_str |
Universidade Estadual Paulista (UNESP) |
instacron_str |
UNESP |
institution |
UNESP |
reponame_str |
Repositório Institucional da UNESP |
collection |
Repositório Institucional da UNESP |
repository.name.fl_str_mv |
Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
repository.mail.fl_str_mv |
|
_version_ |
1808129315785670656 |