Infrared spectra of pyrazine, pyrimidine and pyridazine in solid argon
Autor(a) principal: | |
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Data de Publicação: | 2006 |
Outros Autores: | , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10316/5090 https://doi.org/10.1016/j.molstruc.2005.09.010 |
Resumo: | The vibrational spectra of monomeric diazines (pyrazine, pyrimidine and pyridazine) isolated in solid argon and of the neat crystalline phase of these compounds, at 10 K, are reported and discussed. Full assignment of the spectra is presented, providing evidence that the assignments of several bands previously undertaken for the compounds under other experimental conditions (e.g., gas phase, neat liquid or solution) shall be reconsidered. The interpretation of the experimental data is supported by extensive DFT calculations performed with the B3LYP functional and the 6-311++G(d,p) basis set and by comparison with the anharmonic vibrational calculations reported by Boese and Martin [J.Phys.Chem. A, 108 (2004) 3085] and Berezin et al. [Russian J.Phys.Chem., 79 (2005) 425; Opt.Spectrosc., 97 (2004) 201]. Spectra/structure correlations were extracted from the data, enabling to conclude that, while the [pi]-electron systems in both pyrazine and pyrimidine rings are strongly delocalized over all heavy-atoms, in pyridazine the canonical form with one CC and two CN double bonds strongly predominates. Finally, the UV-induced photoisomerization of matrix isolated monomeric pyrazine to pyrimidine is reported. |
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Infrared spectra of pyrazine, pyrimidine and pyridazine in solid argonPyridazinePyrimidinePyrazineMatrix isolationIR spectroscopyPhotolysisThe vibrational spectra of monomeric diazines (pyrazine, pyrimidine and pyridazine) isolated in solid argon and of the neat crystalline phase of these compounds, at 10 K, are reported and discussed. Full assignment of the spectra is presented, providing evidence that the assignments of several bands previously undertaken for the compounds under other experimental conditions (e.g., gas phase, neat liquid or solution) shall be reconsidered. The interpretation of the experimental data is supported by extensive DFT calculations performed with the B3LYP functional and the 6-311++G(d,p) basis set and by comparison with the anharmonic vibrational calculations reported by Boese and Martin [J.Phys.Chem. A, 108 (2004) 3085] and Berezin et al. [Russian J.Phys.Chem., 79 (2005) 425; Opt.Spectrosc., 97 (2004) 201]. Spectra/structure correlations were extracted from the data, enabling to conclude that, while the [pi]-electron systems in both pyrazine and pyrimidine rings are strongly delocalized over all heavy-atoms, in pyridazine the canonical form with one CC and two CN double bonds strongly predominates. Finally, the UV-induced photoisomerization of matrix isolated monomeric pyrazine to pyrimidine is reported.http://www.sciencedirect.com/science/article/B6TGS-4HDGBX8-2/1/ffab18c394fe2de84bde7bdedcc734662006info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleaplication/PDFhttp://hdl.handle.net/10316/5090http://hdl.handle.net/10316/5090https://doi.org/10.1016/j.molstruc.2005.09.010engJournal of Molecular Structure. 786:2-3 (2006) 193-206Breda, S.Reva, I. D.Lapinski, L.Nowak, M. J.Fausto, R.info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2021-10-04T10:41:25Zoai:estudogeral.uc.pt:10316/5090Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:31.746676Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Infrared spectra of pyrazine, pyrimidine and pyridazine in solid argon |
title |
Infrared spectra of pyrazine, pyrimidine and pyridazine in solid argon |
spellingShingle |
Infrared spectra of pyrazine, pyrimidine and pyridazine in solid argon Breda, S. Pyridazine Pyrimidine Pyrazine Matrix isolation IR spectroscopy Photolysis |
title_short |
Infrared spectra of pyrazine, pyrimidine and pyridazine in solid argon |
title_full |
Infrared spectra of pyrazine, pyrimidine and pyridazine in solid argon |
title_fullStr |
Infrared spectra of pyrazine, pyrimidine and pyridazine in solid argon |
title_full_unstemmed |
Infrared spectra of pyrazine, pyrimidine and pyridazine in solid argon |
title_sort |
Infrared spectra of pyrazine, pyrimidine and pyridazine in solid argon |
author |
Breda, S. |
author_facet |
Breda, S. Reva, I. D. Lapinski, L. Nowak, M. J. Fausto, R. |
author_role |
author |
author2 |
Reva, I. D. Lapinski, L. Nowak, M. J. Fausto, R. |
author2_role |
author author author author |
dc.contributor.author.fl_str_mv |
Breda, S. Reva, I. D. Lapinski, L. Nowak, M. J. Fausto, R. |
dc.subject.por.fl_str_mv |
Pyridazine Pyrimidine Pyrazine Matrix isolation IR spectroscopy Photolysis |
topic |
Pyridazine Pyrimidine Pyrazine Matrix isolation IR spectroscopy Photolysis |
description |
The vibrational spectra of monomeric diazines (pyrazine, pyrimidine and pyridazine) isolated in solid argon and of the neat crystalline phase of these compounds, at 10 K, are reported and discussed. Full assignment of the spectra is presented, providing evidence that the assignments of several bands previously undertaken for the compounds under other experimental conditions (e.g., gas phase, neat liquid or solution) shall be reconsidered. The interpretation of the experimental data is supported by extensive DFT calculations performed with the B3LYP functional and the 6-311++G(d,p) basis set and by comparison with the anharmonic vibrational calculations reported by Boese and Martin [J.Phys.Chem. A, 108 (2004) 3085] and Berezin et al. [Russian J.Phys.Chem., 79 (2005) 425; Opt.Spectrosc., 97 (2004) 201]. Spectra/structure correlations were extracted from the data, enabling to conclude that, while the [pi]-electron systems in both pyrazine and pyrimidine rings are strongly delocalized over all heavy-atoms, in pyridazine the canonical form with one CC and two CN double bonds strongly predominates. Finally, the UV-induced photoisomerization of matrix isolated monomeric pyrazine to pyrimidine is reported. |
publishDate |
2006 |
dc.date.none.fl_str_mv |
2006 |
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://hdl.handle.net/10316/5090 http://hdl.handle.net/10316/5090 https://doi.org/10.1016/j.molstruc.2005.09.010 |
url |
http://hdl.handle.net/10316/5090 https://doi.org/10.1016/j.molstruc.2005.09.010 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Journal of Molecular Structure. 786:2-3 (2006) 193-206 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
aplication/PDF |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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