Microsolvation of morpholine, a bidentate base: the importance of cooperativity

Autores
Vallejos, Margarita; Lamsabhi, Al Mokhtar; Peruchena, Nelida Maria; Mó, Otilia; Yáñes, Manuel
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The structure, relative energies and bonding in morpholine(water)n (n = 1-4) clusters have beeninvestigated at the B3LYP/6-311+G(3df,2p)//B3LYP/6-311+G(d,p) level of theory. Cooperative effects have been analyzed through the use of structural, energetic and electron density indexes. Our analysis shows that these effects are crucial to trace the relative stability of the complexes formed. In all cases water molecules prefer to self-associate forming chains in which each individual molecule behaves as a HB donor and HB acceptor. The chain so formed behaves in turn as HB donor and HB acceptor with respect to morpholine, being the most stable arrangements those in which the NH group of morpholine behaves simultaneously as HB donor and HB acceptor. Higher in energy lie complexes in which the HB acceptor continues to be the NH group, but the HB donor is a CH group, or alternative structures in which the HB acceptor is the ether-like oxygen of morpholine and the HB donor its NH group.  Cooperativity increases with the number of solvent molecules, but there is a clear attenuation effect. Thus, whereas the additive interaction energy on going from dihydrated to trihydrated species increases by a factor of 3, this increase is about half on going from trihydrated to tetrahydrated complexes.
Fil: Vallejos, Margarita. 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: Lamsabhi, Al Mokhtar. Universidad Autónoma de Madrid. Facultad de Ciencias; España
Fil: Peruchena, Nelida Maria. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Mó, Otilia. Universidad Autónoma de Madrid. Facultad de Ciencias; España
Fil: Yáñes, Manuel. Universidad Autónoma de Madrid. Facultad de Ciencias.Departamento de Química; España
Materia
DENSITY FUNCTIONAL THEORY
HERTEROCYCLIC COMPOUNDS
HYDROGEN BOND
MICROSOLVATION
QUANTUM THEORY OF ATOMS IN MOLECULES (QTAIM)
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:11336/106473
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/106473
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Microsolvation of morpholine, a bidentate base: the importance of cooperativityVallejos, MargaritaLamsabhi, Al MokhtarPeruchena, Nelida MariaMó, OtiliaYáñes, ManuelDENSITY FUNCTIONAL THEORYHERTEROCYCLIC COMPOUNDSHYDROGEN BONDMICROSOLVATIONQUANTUM THEORY OF ATOMS IN MOLECULES (QTAIM)https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The structure, relative energies and bonding in morpholine(water)n (n = 1-4) clusters have beeninvestigated at the B3LYP/6-311+G(3df,2p)//B3LYP/6-311+G(d,p) level of theory. Cooperative effects have been analyzed through the use of structural, energetic and electron density indexes. Our analysis shows that these effects are crucial to trace the relative stability of the complexes formed. In all cases water molecules prefer to self-associate forming chains in which each individual molecule behaves as a HB donor and HB acceptor. The chain so formed behaves in turn as HB donor and HB acceptor with respect to morpholine, being the most stable arrangements those in which the NH group of morpholine behaves simultaneously as HB donor and HB acceptor. Higher in energy lie complexes in which the HB acceptor continues to be the NH group, but the HB donor is a CH group, or alternative structures in which the HB acceptor is the ether-like oxygen of morpholine and the HB donor its NH group.  Cooperativity increases with the number of solvent molecules, but there is a clear attenuation effect. Thus, whereas the additive interaction energy on going from dihydrated to trihydrated species increases by a factor of 3, this increase is about half on going from trihydrated to tetrahydrated complexes.Fil: Vallejos, Margarita. 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: Lamsabhi, Al Mokhtar. Universidad Autónoma de Madrid. Facultad de Ciencias; EspañaFil: Peruchena, Nelida Maria. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Mó, Otilia. Universidad Autónoma de Madrid. Facultad de Ciencias; EspañaFil: Yáñes, Manuel. Universidad Autónoma de Madrid. Facultad de Ciencias.Departamento de Química; EspañaJohn Wiley & Sons Ltd2012-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/106473Vallejos, Margarita; Lamsabhi, Al Mokhtar; Peruchena, Nelida Maria; Mó, Otilia; Yáñes, Manuel; Microsolvation of morpholine, a bidentate base: the importance of cooperativity; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 25; 12; 12-2012; 1380-13900894-3230CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/poc.3053info:eu-repo/semantics/altIdentifier/doi/10.1002/poc.3053info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:44:40Zoai:ri.conicet.gov.ar:11336/106473instacron: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 10:44:40.765CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Microsolvation of morpholine, a bidentate base: the importance of cooperativity
title Microsolvation of morpholine, a bidentate base: the importance of cooperativity
spellingShingle Microsolvation of morpholine, a bidentate base: the importance of cooperativity
Vallejos, Margarita
DENSITY FUNCTIONAL THEORY
HERTEROCYCLIC COMPOUNDS
HYDROGEN BOND
MICROSOLVATION
QUANTUM THEORY OF ATOMS IN MOLECULES (QTAIM)
title_short Microsolvation of morpholine, a bidentate base: the importance of cooperativity
title_full Microsolvation of morpholine, a bidentate base: the importance of cooperativity
title_fullStr Microsolvation of morpholine, a bidentate base: the importance of cooperativity
title_full_unstemmed Microsolvation of morpholine, a bidentate base: the importance of cooperativity
title_sort Microsolvation of morpholine, a bidentate base: the importance of cooperativity
dc.creator.none.fl_str_mv Vallejos, Margarita
Lamsabhi, Al Mokhtar
Peruchena, Nelida Maria
Mó, Otilia
Yáñes, Manuel
author Vallejos, Margarita
author_facet Vallejos, Margarita
Lamsabhi, Al Mokhtar
Peruchena, Nelida Maria
Mó, Otilia
Yáñes, Manuel
author_role author
author2 Lamsabhi, Al Mokhtar
Peruchena, Nelida Maria
Mó, Otilia
Yáñes, Manuel
author2_role author
author
author
author
dc.subject.none.fl_str_mv DENSITY FUNCTIONAL THEORY
HERTEROCYCLIC COMPOUNDS
HYDROGEN BOND
MICROSOLVATION
QUANTUM THEORY OF ATOMS IN MOLECULES (QTAIM)
topic DENSITY FUNCTIONAL THEORY
HERTEROCYCLIC COMPOUNDS
HYDROGEN BOND
MICROSOLVATION
QUANTUM THEORY OF ATOMS IN MOLECULES (QTAIM)
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The structure, relative energies and bonding in morpholine(water)n (n = 1-4) clusters have beeninvestigated at the B3LYP/6-311+G(3df,2p)//B3LYP/6-311+G(d,p) level of theory. Cooperative effects have been analyzed through the use of structural, energetic and electron density indexes. Our analysis shows that these effects are crucial to trace the relative stability of the complexes formed. In all cases water molecules prefer to self-associate forming chains in which each individual molecule behaves as a HB donor and HB acceptor. The chain so formed behaves in turn as HB donor and HB acceptor with respect to morpholine, being the most stable arrangements those in which the NH group of morpholine behaves simultaneously as HB donor and HB acceptor. Higher in energy lie complexes in which the HB acceptor continues to be the NH group, but the HB donor is a CH group, or alternative structures in which the HB acceptor is the ether-like oxygen of morpholine and the HB donor its NH group.  Cooperativity increases with the number of solvent molecules, but there is a clear attenuation effect. Thus, whereas the additive interaction energy on going from dihydrated to trihydrated species increases by a factor of 3, this increase is about half on going from trihydrated to tetrahydrated complexes.
Fil: Vallejos, Margarita. 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: Lamsabhi, Al Mokhtar. Universidad Autónoma de Madrid. Facultad de Ciencias; España
Fil: Peruchena, Nelida Maria. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Mó, Otilia. Universidad Autónoma de Madrid. Facultad de Ciencias; España
Fil: Yáñes, Manuel. Universidad Autónoma de Madrid. Facultad de Ciencias.Departamento de Química; España
description The structure, relative energies and bonding in morpholine(water)n (n = 1-4) clusters have beeninvestigated at the B3LYP/6-311+G(3df,2p)//B3LYP/6-311+G(d,p) level of theory. Cooperative effects have been analyzed through the use of structural, energetic and electron density indexes. Our analysis shows that these effects are crucial to trace the relative stability of the complexes formed. In all cases water molecules prefer to self-associate forming chains in which each individual molecule behaves as a HB donor and HB acceptor. The chain so formed behaves in turn as HB donor and HB acceptor with respect to morpholine, being the most stable arrangements those in which the NH group of morpholine behaves simultaneously as HB donor and HB acceptor. Higher in energy lie complexes in which the HB acceptor continues to be the NH group, but the HB donor is a CH group, or alternative structures in which the HB acceptor is the ether-like oxygen of morpholine and the HB donor its NH group.  Cooperativity increases with the number of solvent molecules, but there is a clear attenuation effect. Thus, whereas the additive interaction energy on going from dihydrated to trihydrated species increases by a factor of 3, this increase is about half on going from trihydrated to tetrahydrated complexes.
publishDate 2012
dc.date.none.fl_str_mv 2012-12
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/11336/106473
Vallejos, Margarita; Lamsabhi, Al Mokhtar; Peruchena, Nelida Maria; Mó, Otilia; Yáñes, Manuel; Microsolvation of morpholine, a bidentate base: the importance of cooperativity; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 25; 12; 12-2012; 1380-1390
0894-3230
CONICET Digital
CONICET
url http://hdl.handle.net/11336/106473
identifier_str_mv Vallejos, Margarita; Lamsabhi, Al Mokhtar; Peruchena, Nelida Maria; Mó, Otilia; Yáñes, Manuel; Microsolvation of morpholine, a bidentate base: the importance of cooperativity; John Wiley & Sons Ltd; Journal Of Physical Organic Chemistry; 25; 12; 12-2012; 1380-1390
0894-3230
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/poc.3053
info:eu-repo/semantics/altIdentifier/doi/10.1002/poc.3053
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 John Wiley & Sons Ltd
publisher.none.fl_str_mv John Wiley & Sons Ltd
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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score 13.070432

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