Mending ties with halogens: HALO–DP4+: an approach for DP4+ calculations in organohalogenated molecules

Autores
Passaglia, Lucas; Franco, Bruno A.; Zanardi, María M.; Sarotti, Ariel M.
Año de publicación
2025
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Fil: Passaglia, Lucas. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; Argentina
Fil: Franco, Bruno A. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; Argentina
Fil: Zanardi, María M. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; Argentina
Fil: Sarotti, Ariel M. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
The combined use of NMR spectroscopy and quantum chemical calculations has become a powerful strategy for structural elucidation. However, halogenated compounds pose a particular challenge due to the so-called HALA effect, where heavy atoms distort the shielding of nearby light atoms, often leading to misleading predictions. Although a common workaround is to discard affected signals, this approach fails in polyhalogenated systems, where too much valuable information is lost. In this study, we systematically explored a range of strategies to mitigate the HALA effect across different levels of theory and probability-based methods: DP4, MM-DP4+, and DP4+. This comprehensive analysis led us to develop HALO–DP4+, a simple yet robust correction protocol that significantly improves performance and can be universally applied regardless level of theory used. To streamline its use, we updated our DP4+App to fully automate the correction process, making HALO–DP4+ readily accessible for routine structure determination, even in challenging halogenated frameworks.
Fuente
The Journal of Organic Chemistry, vol. 90, n. 44, pp. 15737–15747
Materia
QUIMICA COMPUTACIONAL
HALOGENOS
ESPECTROSCOPIA
DP4
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
Repositorio Institucional (UCA)
Institución
Pontificia Universidad Católica Argentina
OAI Identificador
oai:ucacris:123456789/22054
Acceder
id RIUCA_ce9c18ffe377b0ac25afbc59e0b63806
oai_identifier_str oai:ucacris:123456789/22054
network_acronym_str RIUCA
repository_id_str 2585
network_name_str Repositorio Institucional (UCA)
spelling Mending ties with halogens: HALO–DP4+: an approach for DP4+ calculations in organohalogenated moleculesPassaglia, LucasFranco, Bruno A.Zanardi, María M.Sarotti, Ariel M.QUIMICA COMPUTACIONALHALOGENOSESPECTROSCOPIADP4Fil: Passaglia, Lucas. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; ArgentinaFil: Franco, Bruno A. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; ArgentinaFil: Zanardi, María M. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; ArgentinaFil: Sarotti, Ariel M. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaThe combined use of NMR spectroscopy and quantum chemical calculations has become a powerful strategy for structural elucidation. However, halogenated compounds pose a particular challenge due to the so-called HALA effect, where heavy atoms distort the shielding of nearby light atoms, often leading to misleading predictions. Although a common workaround is to discard affected signals, this approach fails in polyhalogenated systems, where too much valuable information is lost. In this study, we systematically explored a range of strategies to mitigate the HALA effect across different levels of theory and probability-based methods: DP4, MM-DP4+, and DP4+. This comprehensive analysis led us to develop HALO–DP4+, a simple yet robust correction protocol that significantly improves performance and can be universally applied regardless level of theory used. To streamline its use, we updated our DP4+App to fully automate the correction process, making HALO–DP4+ readily accessible for routine structure determination, even in challenging halogenated frameworks.American Chemical Society2025info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfhttps://repositorio.uca.edu.ar/handle/123456789/220540022-326310.1021/acs.joc.5c01979The Journal of Organic Chemistry, vol. 90, n. 44, pp. 15737–15747reponame:Repositorio Institucional (UCA)instname:Pontificia Universidad Católica Argentinaenginfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/4.0/2026-10-01T12:03:37Zoai:ucacris:123456789/22054instacron:UCAInstitucionalhttps://repositorio.uca.edu.ar/Universidad privadaNo correspondehttps://repositorio.uca.edu.ar/oaiclaudia_fernandez@uca.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:25852026-10-01 12:03:38.055Repositorio Institucional (UCA) - Pontificia Universidad Católica Argentinafalse
dc.title.none.fl_str_mv Mending ties with halogens: HALO–DP4+: an approach for DP4+ calculations in organohalogenated molecules
title Mending ties with halogens: HALO–DP4+: an approach for DP4+ calculations in organohalogenated molecules
spellingShingle Mending ties with halogens: HALO–DP4+: an approach for DP4+ calculations in organohalogenated molecules
Passaglia, Lucas
QUIMICA COMPUTACIONAL
HALOGENOS
ESPECTROSCOPIA
DP4
title_short Mending ties with halogens: HALO–DP4+: an approach for DP4+ calculations in organohalogenated molecules
title_full Mending ties with halogens: HALO–DP4+: an approach for DP4+ calculations in organohalogenated molecules
title_fullStr Mending ties with halogens: HALO–DP4+: an approach for DP4+ calculations in organohalogenated molecules
title_full_unstemmed Mending ties with halogens: HALO–DP4+: an approach for DP4+ calculations in organohalogenated molecules
title_sort Mending ties with halogens: HALO–DP4+: an approach for DP4+ calculations in organohalogenated molecules
dc.creator.none.fl_str_mv Passaglia, Lucas
Franco, Bruno A.
Zanardi, María M.
Sarotti, Ariel M.
author Passaglia, Lucas
author_facet Passaglia, Lucas
Franco, Bruno A.
Zanardi, María M.
Sarotti, Ariel M.
author_role author
author2 Franco, Bruno A.
Zanardi, María M.
Sarotti, Ariel M.
author2_role author
author
author
dc.subject.none.fl_str_mv QUIMICA COMPUTACIONAL
HALOGENOS
ESPECTROSCOPIA
DP4
topic QUIMICA COMPUTACIONAL
HALOGENOS
ESPECTROSCOPIA
DP4
dc.description.none.fl_txt_mv Fil: Passaglia, Lucas. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; Argentina
Fil: Franco, Bruno A. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; Argentina
Fil: Zanardi, María M. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; Argentina
Fil: Sarotti, Ariel M. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
The combined use of NMR spectroscopy and quantum chemical calculations has become a powerful strategy for structural elucidation. However, halogenated compounds pose a particular challenge due to the so-called HALA effect, where heavy atoms distort the shielding of nearby light atoms, often leading to misleading predictions. Although a common workaround is to discard affected signals, this approach fails in polyhalogenated systems, where too much valuable information is lost. In this study, we systematically explored a range of strategies to mitigate the HALA effect across different levels of theory and probability-based methods: DP4, MM-DP4+, and DP4+. This comprehensive analysis led us to develop HALO–DP4+, a simple yet robust correction protocol that significantly improves performance and can be universally applied regardless level of theory used. To streamline its use, we updated our DP4+App to fully automate the correction process, making HALO–DP4+ readily accessible for routine structure determination, even in challenging halogenated frameworks.
description Fil: Passaglia, Lucas. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario. Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada; Argentina
publishDate 2025
dc.date.none.fl_str_mv 2025
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 https://repositorio.uca.edu.ar/handle/123456789/22054
0022-3263
10.1021/acs.joc.5c01979
url https://repositorio.uca.edu.ar/handle/123456789/22054
identifier_str_mv 0022-3263
10.1021/acs.joc.5c01979
dc.language.none.fl_str_mv eng
language eng
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/4.0/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/4.0/
dc.format.none.fl_str_mv 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 The Journal of Organic Chemistry, vol. 90, n. 44, pp. 15737–15747
reponame:Repositorio Institucional (UCA)
instname:Pontificia Universidad Católica Argentina
reponame_str Repositorio Institucional (UCA)
collection Repositorio Institucional (UCA)
instname_str Pontificia Universidad Católica Argentina
repository.name.fl_str_mv Repositorio Institucional (UCA) - Pontificia Universidad Católica Argentina
repository.mail.fl_str_mv claudia_fernandez@uca.edu.ar
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score 12.853507

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