Through-Bond and Through-Space Interactions in [2,2]Cyclophanes
Autor(a) principal: | |
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Data de Publicação: | 2021 |
Outros Autores: | , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Journal of the Brazilian Chemical Society (Online) |
Texto Completo: | http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532021000701447 |
Resumo: | The interpretation of the distortions of the electron distribution in [2,2]cyclophanes (22-CPs) is controversial. Some studies indicate that there is an accumulation of electron density (ρ) outside the cavity of 22-CPs. The nature of through-space (ts) interaction is still under debate. The relative importance of ts and through-bond (tb) is an open question. In an attempt to clarify these points, we have investigated five 22-CPs and their corresponding toluene dimers by molecular orbitals analysis, electron density difference analysis, some topological analysis of ρ (quantum theory of atoms in molecules (QTAIM), electron localization function (ELF) and noncovalent interactions (NCI)), and energy decomposition analysis with natural orbitals for chemical valence (EDA-NOCV). ρ is concentrated inside the inter-ring region. All the analyses indicated that ts is predominant. The ts is composed by attractive dispersion and Pauli repulsion, with a small covalent contribution. Except for 1 and 6, all the compounds present inter-ring bond paths. |
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Through-Bond and Through-Space Interactions in [2,2]Cyclophanes[2,2]cyclophanesthrough bond interactionthrough space interactionnon-covalent interactioninteracting quantum atoms (IQA)The interpretation of the distortions of the electron distribution in [2,2]cyclophanes (22-CPs) is controversial. Some studies indicate that there is an accumulation of electron density (ρ) outside the cavity of 22-CPs. The nature of through-space (ts) interaction is still under debate. The relative importance of ts and through-bond (tb) is an open question. In an attempt to clarify these points, we have investigated five 22-CPs and their corresponding toluene dimers by molecular orbitals analysis, electron density difference analysis, some topological analysis of ρ (quantum theory of atoms in molecules (QTAIM), electron localization function (ELF) and noncovalent interactions (NCI)), and energy decomposition analysis with natural orbitals for chemical valence (EDA-NOCV). ρ is concentrated inside the inter-ring region. All the analyses indicated that ts is predominant. The ts is composed by attractive dispersion and Pauli repulsion, with a small covalent contribution. Except for 1 and 6, all the compounds present inter-ring bond paths.Sociedade Brasileira de Química2021-07-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532021000701447Journal of the Brazilian Chemical Society v.32 n.7 2021reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.21577/0103-5053.20210043info:eu-repo/semantics/openAccessGalembeck,Sérgio E.Orenha,Renato P.Madeira,Rafael M.Peixoto,Letícia B.Parreira,Renato L. T.eng2021-06-30T00:00:00Zoai:scielo:S0103-50532021000701447Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2021-06-30T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false |
dc.title.none.fl_str_mv |
Through-Bond and Through-Space Interactions in [2,2]Cyclophanes |
title |
Through-Bond and Through-Space Interactions in [2,2]Cyclophanes |
spellingShingle |
Through-Bond and Through-Space Interactions in [2,2]Cyclophanes Galembeck,Sérgio E. [2,2]cyclophanes through bond interaction through space interaction non-covalent interaction interacting quantum atoms (IQA) |
title_short |
Through-Bond and Through-Space Interactions in [2,2]Cyclophanes |
title_full |
Through-Bond and Through-Space Interactions in [2,2]Cyclophanes |
title_fullStr |
Through-Bond and Through-Space Interactions in [2,2]Cyclophanes |
title_full_unstemmed |
Through-Bond and Through-Space Interactions in [2,2]Cyclophanes |
title_sort |
Through-Bond and Through-Space Interactions in [2,2]Cyclophanes |
author |
Galembeck,Sérgio E. |
author_facet |
Galembeck,Sérgio E. Orenha,Renato P. Madeira,Rafael M. Peixoto,Letícia B. Parreira,Renato L. T. |
author_role |
author |
author2 |
Orenha,Renato P. Madeira,Rafael M. Peixoto,Letícia B. Parreira,Renato L. T. |
author2_role |
author author author author |
dc.contributor.author.fl_str_mv |
Galembeck,Sérgio E. Orenha,Renato P. Madeira,Rafael M. Peixoto,Letícia B. Parreira,Renato L. T. |
dc.subject.por.fl_str_mv |
[2,2]cyclophanes through bond interaction through space interaction non-covalent interaction interacting quantum atoms (IQA) |
topic |
[2,2]cyclophanes through bond interaction through space interaction non-covalent interaction interacting quantum atoms (IQA) |
description |
The interpretation of the distortions of the electron distribution in [2,2]cyclophanes (22-CPs) is controversial. Some studies indicate that there is an accumulation of electron density (ρ) outside the cavity of 22-CPs. The nature of through-space (ts) interaction is still under debate. The relative importance of ts and through-bond (tb) is an open question. In an attempt to clarify these points, we have investigated five 22-CPs and their corresponding toluene dimers by molecular orbitals analysis, electron density difference analysis, some topological analysis of ρ (quantum theory of atoms in molecules (QTAIM), electron localization function (ELF) and noncovalent interactions (NCI)), and energy decomposition analysis with natural orbitals for chemical valence (EDA-NOCV). ρ is concentrated inside the inter-ring region. All the analyses indicated that ts is predominant. The ts is composed by attractive dispersion and Pauli repulsion, with a small covalent contribution. Except for 1 and 6, all the compounds present inter-ring bond paths. |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-07-01 |
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=S0103-50532021000701447 |
url |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532021000701447 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.21577/0103-5053.20210043 |
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 |
Journal of the Brazilian Chemical Society v.32 n.7 2021 reponame:Journal of the Brazilian Chemical Society (Online) instname:Sociedade Brasileira de Química (SBQ) instacron:SBQ |
instname_str |
Sociedade Brasileira de Química (SBQ) |
instacron_str |
SBQ |
institution |
SBQ |
reponame_str |
Journal of the Brazilian Chemical Society (Online) |
collection |
Journal of the Brazilian Chemical Society (Online) |
repository.name.fl_str_mv |
Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ) |
repository.mail.fl_str_mv |
||office@jbcs.sbq.org.br |
_version_ |
1750318184370536448 |