Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study
Autor(a) principal: | |
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Data de Publicação: | 2003 |
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/10316/17831 https://doi.org/10.1039/B306489A |
Resumo: | Theoretical optimization of triphenylamine geometry, carried out at DFT(B3LYP) level using 6-31G** and aug-cc-pVDZ basis sets, predicted a propeller-like structure of the compound with D3 overall symmetry. In this structure, the central NCCC atoms are coplanar and the phenyl rings are symmetrically twisted from this plane by 41.5° (6-31G**) or 41.6° (aug-cc-pVDZ). The experimental FTIR spectrum of triphenylamine monomers isolated in an argon matrix was measured and interpreted by comparison with theoretical spectra calculated at the DFT(B3LYP) level with 6-31G** or aug-cc-pVDZ basis sets. The good agreement between the experimental and theoretical spectra allowed a positive assignment of the observed infrared absorption bands. Conformational flexibility of triphenylamine was investigated by carrying out a series of theoretical scans of the potential energy hypersurface of the system. Special attention was granted to the minimal energy pathway between the left-hand rotating and right-hand rotating symmetry identical structures of the compound. A route conserving a C2 symmetry axis was identified as implying an energy barrier of 20 kJ mol−1 only, whereas the calculated barrier for the concerted twist of all the phenyl rings (the route with conservation of the C3 symmetry axis) was as high as 54 kJ mol−1. |
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Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical studyTheoretical optimization of triphenylamine geometry, carried out at DFT(B3LYP) level using 6-31G** and aug-cc-pVDZ basis sets, predicted a propeller-like structure of the compound with D3 overall symmetry. In this structure, the central NCCC atoms are coplanar and the phenyl rings are symmetrically twisted from this plane by 41.5° (6-31G**) or 41.6° (aug-cc-pVDZ). The experimental FTIR spectrum of triphenylamine monomers isolated in an argon matrix was measured and interpreted by comparison with theoretical spectra calculated at the DFT(B3LYP) level with 6-31G** or aug-cc-pVDZ basis sets. The good agreement between the experimental and theoretical spectra allowed a positive assignment of the observed infrared absorption bands. Conformational flexibility of triphenylamine was investigated by carrying out a series of theoretical scans of the potential energy hypersurface of the system. Special attention was granted to the minimal energy pathway between the left-hand rotating and right-hand rotating symmetry identical structures of the compound. A route conserving a C2 symmetry axis was identified as implying an energy barrier of 20 kJ mol−1 only, whereas the calculated barrier for the concerted twist of all the phenyl rings (the route with conservation of the C3 symmetry axis) was as high as 54 kJ mol−1.Royal Society of Chemistry2003-08-06info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/17831http://hdl.handle.net/10316/17831https://doi.org/10.1039/B306489AengReva, IgorLapinski, LeszekChattopadhyay, NitinFausto, Ruiinfo: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:RCAAP2020-02-11T18:17:40Zoai:estudogeral.uc.pt:10316/17831Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:44.330570Repositório 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 |
Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study |
title |
Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study |
spellingShingle |
Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study Reva, Igor |
title_short |
Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study |
title_full |
Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study |
title_fullStr |
Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study |
title_full_unstemmed |
Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study |
title_sort |
Vibrational spectrum and molecular structure of triphenylamine monomer: A combined matrix-isolation FTIR and theoretical study |
author |
Reva, Igor |
author_facet |
Reva, Igor Lapinski, Leszek Chattopadhyay, Nitin Fausto, Rui |
author_role |
author |
author2 |
Lapinski, Leszek Chattopadhyay, Nitin Fausto, Rui |
author2_role |
author author author |
dc.contributor.author.fl_str_mv |
Reva, Igor Lapinski, Leszek Chattopadhyay, Nitin Fausto, Rui |
description |
Theoretical optimization of triphenylamine geometry, carried out at DFT(B3LYP) level using 6-31G** and aug-cc-pVDZ basis sets, predicted a propeller-like structure of the compound with D3 overall symmetry. In this structure, the central NCCC atoms are coplanar and the phenyl rings are symmetrically twisted from this plane by 41.5° (6-31G**) or 41.6° (aug-cc-pVDZ). The experimental FTIR spectrum of triphenylamine monomers isolated in an argon matrix was measured and interpreted by comparison with theoretical spectra calculated at the DFT(B3LYP) level with 6-31G** or aug-cc-pVDZ basis sets. The good agreement between the experimental and theoretical spectra allowed a positive assignment of the observed infrared absorption bands. Conformational flexibility of triphenylamine was investigated by carrying out a series of theoretical scans of the potential energy hypersurface of the system. Special attention was granted to the minimal energy pathway between the left-hand rotating and right-hand rotating symmetry identical structures of the compound. A route conserving a C2 symmetry axis was identified as implying an energy barrier of 20 kJ mol−1 only, whereas the calculated barrier for the concerted twist of all the phenyl rings (the route with conservation of the C3 symmetry axis) was as high as 54 kJ mol−1. |
publishDate |
2003 |
dc.date.none.fl_str_mv |
2003-08-06 |
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/10316/17831 http://hdl.handle.net/10316/17831 https://doi.org/10.1039/B306489A |
url |
http://hdl.handle.net/10316/17831 https://doi.org/10.1039/B306489A |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Royal Society of Chemistry |
publisher.none.fl_str_mv |
Royal Society of Chemistry |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
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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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1799133907908558848 |