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
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/63885
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling 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 Técnicas2025-10-22T11:48:09Zoai: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:34982025-10-22 11:48:09.967CONICET 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
_version_ 1846782187059281920
score 12.982451

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