Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation
- Autores
- Terra Martins, Felipe; de Freitas Oliveira, Breno Germano; Sarotti, Ariel Marcelo; de Fátima, Angelo
- Año de publicación
- 2017
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- Hexa-p-tert-butylcalix[6]arene (1) is believed to adopt a winged conformation in a solution, featured by four phenyl rings perpendicular to the calix basis and two others at 1,4-positions lying down. However, there is some controversy on the occurrence of this conformation because it has never been found in the solid state of calix[6]arenes, regardless of the substitution pattern at lower and upper rims. Here, we have observed the winged-cone conformation for the first time in a solvate form of 1 with dimethyl sulfoxide (DMSO), dimethylformamide, and pyridine. The DMSO molecule is strongly encapsulated into 1 through two OH···O hydrogen bonds with both flattened phenolic moieties, one lp(S) ···π and four CH···π interactions with the four perpendicular phenyl rings. This host-guest complex has energy lower by 23.4 kcal mol-1 than the isolated species. In addition, another DMSO solvate form with 1,2,3-alternate conformation was also obtained in this study, and its structure is compared with that of the precedent one. A detailed density functional theory study has also been carried out to understand the energetic relationships among cone conformers, intramolecular hydrogen-bonding patterns, and DMSO encapsulation.
Fil: Terra Martins, Felipe. Universidade Federal de Goiás; Brasil
Fil: de Freitas Oliveira, Breno Germano. Universidade Federal de Minas Gerais; Brasil
Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
Fil: de Fátima, Angelo. Universidade Federal de Minas Gerais; Brasil - Materia
-
WINGED-CONE CONFORMATION
CALIX[6]ARENE
GUEST ENCAPSULATION
DFT CALCULATIONS - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/63885
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Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulationTerra Martins, Felipede Freitas Oliveira, Breno GermanoSarotti, Ariel Marcelode Fátima, AngeloWINGED-CONE CONFORMATIONCALIX[6]ARENEGUEST ENCAPSULATIONDFT CALCULATIONShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Hexa-p-tert-butylcalix[6]arene (1) is believed to adopt a winged conformation in a solution, featured by four phenyl rings perpendicular to the calix basis and two others at 1,4-positions lying down. However, there is some controversy on the occurrence of this conformation because it has never been found in the solid state of calix[6]arenes, regardless of the substitution pattern at lower and upper rims. Here, we have observed the winged-cone conformation for the first time in a solvate form of 1 with dimethyl sulfoxide (DMSO), dimethylformamide, and pyridine. The DMSO molecule is strongly encapsulated into 1 through two OH···O hydrogen bonds with both flattened phenolic moieties, one lp(S) ···π and four CH···π interactions with the four perpendicular phenyl rings. This host-guest complex has energy lower by 23.4 kcal mol-1 than the isolated species. In addition, another DMSO solvate form with 1,2,3-alternate conformation was also obtained in this study, and its structure is compared with that of the precedent one. A detailed density functional theory study has also been carried out to understand the energetic relationships among cone conformers, intramolecular hydrogen-bonding patterns, and DMSO encapsulation.Fil: Terra Martins, Felipe. Universidade Federal de Goiás; BrasilFil: de Freitas Oliveira, Breno Germano. Universidade Federal de Minas Gerais; BrasilFil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaFil: de Fátima, Angelo. Universidade Federal de Minas Gerais; BrasilAmerican Chemical Society2017-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/63885Terra Martins, Felipe; de Freitas Oliveira, Breno Germano; Sarotti, Ariel Marcelo; de Fátima, Angelo; Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation; American Chemical Society; ACS Omega; 2; 8; 8-2017; 5315-53232470-1343CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acsomega.7b00900info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acsomega.7b00900info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:17:48Zoai:ri.conicet.gov.ar:11336/63885instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:17:49.256CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
dc.title.none.fl_str_mv |
Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation |
title |
Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation |
spellingShingle |
Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation Terra Martins, Felipe WINGED-CONE CONFORMATION CALIX[6]ARENE GUEST ENCAPSULATION DFT CALCULATIONS |
title_short |
Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation |
title_full |
Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation |
title_fullStr |
Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation |
title_full_unstemmed |
Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation |
title_sort |
Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation |
dc.creator.none.fl_str_mv |
Terra Martins, Felipe de Freitas Oliveira, Breno Germano Sarotti, Ariel Marcelo de Fátima, Angelo |
author |
Terra Martins, Felipe |
author_facet |
Terra Martins, Felipe de Freitas Oliveira, Breno Germano Sarotti, Ariel Marcelo de Fátima, Angelo |
author_role |
author |
author2 |
de Freitas Oliveira, Breno Germano Sarotti, Ariel Marcelo de Fátima, Angelo |
author2_role |
author author author |
dc.subject.none.fl_str_mv |
WINGED-CONE CONFORMATION CALIX[6]ARENE GUEST ENCAPSULATION DFT CALCULATIONS |
topic |
WINGED-CONE CONFORMATION CALIX[6]ARENE GUEST ENCAPSULATION DFT CALCULATIONS |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
Hexa-p-tert-butylcalix[6]arene (1) is believed to adopt a winged conformation in a solution, featured by four phenyl rings perpendicular to the calix basis and two others at 1,4-positions lying down. However, there is some controversy on the occurrence of this conformation because it has never been found in the solid state of calix[6]arenes, regardless of the substitution pattern at lower and upper rims. Here, we have observed the winged-cone conformation for the first time in a solvate form of 1 with dimethyl sulfoxide (DMSO), dimethylformamide, and pyridine. The DMSO molecule is strongly encapsulated into 1 through two OH···O hydrogen bonds with both flattened phenolic moieties, one lp(S) ···π and four CH···π interactions with the four perpendicular phenyl rings. This host-guest complex has energy lower by 23.4 kcal mol-1 than the isolated species. In addition, another DMSO solvate form with 1,2,3-alternate conformation was also obtained in this study, and its structure is compared with that of the precedent one. A detailed density functional theory study has also been carried out to understand the energetic relationships among cone conformers, intramolecular hydrogen-bonding patterns, and DMSO encapsulation. Fil: Terra Martins, Felipe. Universidade Federal de Goiás; Brasil Fil: de Freitas Oliveira, Breno Germano. Universidade Federal de Minas Gerais; Brasil Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina Fil: de Fátima, Angelo. Universidade Federal de Minas Gerais; Brasil |
description |
Hexa-p-tert-butylcalix[6]arene (1) is believed to adopt a winged conformation in a solution, featured by four phenyl rings perpendicular to the calix basis and two others at 1,4-positions lying down. However, there is some controversy on the occurrence of this conformation because it has never been found in the solid state of calix[6]arenes, regardless of the substitution pattern at lower and upper rims. Here, we have observed the winged-cone conformation for the first time in a solvate form of 1 with dimethyl sulfoxide (DMSO), dimethylformamide, and pyridine. The DMSO molecule is strongly encapsulated into 1 through two OH···O hydrogen bonds with both flattened phenolic moieties, one lp(S) ···π and four CH···π interactions with the four perpendicular phenyl rings. This host-guest complex has energy lower by 23.4 kcal mol-1 than the isolated species. In addition, another DMSO solvate form with 1,2,3-alternate conformation was also obtained in this study, and its structure is compared with that of the precedent one. A detailed density functional theory study has also been carried out to understand the energetic relationships among cone conformers, intramolecular hydrogen-bonding patterns, and DMSO encapsulation. |
publishDate |
2017 |
dc.date.none.fl_str_mv |
2017-08 |
dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
status_str |
publishedVersion |
dc.identifier.none.fl_str_mv |
http://hdl.handle.net/11336/63885 Terra Martins, Felipe; de Freitas Oliveira, Breno Germano; Sarotti, Ariel Marcelo; de Fátima, Angelo; Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation; American Chemical Society; ACS Omega; 2; 8; 8-2017; 5315-5323 2470-1343 CONICET Digital CONICET |
url |
http://hdl.handle.net/11336/63885 |
identifier_str_mv |
Terra Martins, Felipe; de Freitas Oliveira, Breno Germano; Sarotti, Ariel Marcelo; de Fátima, Angelo; Winged-cone conformation in hexa-p-tert-butylcalix[6]arene driven by the unusually strong guest encapsulation; American Chemical Society; ACS Omega; 2; 8; 8-2017; 5315-5323 2470-1343 CONICET Digital CONICET |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/doi/10.1021/acsomega.7b00900 info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acsomega.7b00900 |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
dc.format.none.fl_str_mv |
application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
American Chemical Society |
publisher.none.fl_str_mv |
American Chemical Society |
dc.source.none.fl_str_mv |
reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
reponame_str |
CONICET Digital (CONICET) |
collection |
CONICET Digital (CONICET) |
instname_str |
Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.name.fl_str_mv |
CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
repository.mail.fl_str_mv |
dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
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1844614134467919872 |
score |
13.070432 |