Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes

Autores
Riebe, Jan; Bädorf, Benedikt; Löffelsender, Sarah; Gutierrez Suburu, Matias Ezequiel; Rivas Aiello, Maria Belen; Strassert, Cristian A.; Grimme, Stefan; Niemeyer, Jochen
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Rotaxanes are mechanically interlocked molecules where a ring (macrocycle) is threaded onto a linearmolecule (thread). The position of the macrocycle on different stations on the thread can be controlledin response to external stimuli, making rotaxanes applicable as molecular switches. Here we show that bistable rotaxanes based on the combination of a Zn(II) tetraphenylporphyrin photosensitizer,attached to the macrocycle, and a black-hole-quencher, attached to the thread, are capable of singletoxygen production which can be switched on/off by the addition of base/acid. However, we found thatonly a sufficiently long linker between both stations on the thread enabled switchability, and that thedirection of switching was inversed with regard to the original design. This unexpected behavior wasattributed to intramolecular folding of the rotaxanes, as indicated by extensive theoretical calculations.This evidences the importance to take into account the conformational flexibility of large molecularstructures when designing functional switchable systems.
Fil: Riebe, Jan. Universitat Essen; Alemania
Fil: Bädorf, Benedikt. Universitat Bonn; Alemania
Fil: Löffelsender, Sarah. Universitat Bonn; Alemania
Fil: Gutierrez Suburu, Matias Ezequiel. Universität Münster; Alemania
Fil: Rivas Aiello, Maria Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Strassert, Cristian A.. Universität Münster; Alemania
Fil: Grimme, Stefan. Universitat Bonn; Alemania
Fil: Niemeyer, Jochen. Universitat Essen; Alemania
Materia
ROTAXANES
SINGLET OXYGEN
PORPHYRIN
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:11336/263581
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanesRiebe, JanBädorf, BenediktLöffelsender, SarahGutierrez Suburu, Matias EzequielRivas Aiello, Maria BelenStrassert, Cristian A.Grimme, StefanNiemeyer, JochenROTAXANESSINGLET OXYGENPORPHYRINhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Rotaxanes are mechanically interlocked molecules where a ring (macrocycle) is threaded onto a linearmolecule (thread). The position of the macrocycle on different stations on the thread can be controlledin response to external stimuli, making rotaxanes applicable as molecular switches. Here we show that bistable rotaxanes based on the combination of a Zn(II) tetraphenylporphyrin photosensitizer,attached to the macrocycle, and a black-hole-quencher, attached to the thread, are capable of singletoxygen production which can be switched on/off by the addition of base/acid. However, we found thatonly a sufficiently long linker between both stations on the thread enabled switchability, and that thedirection of switching was inversed with regard to the original design. This unexpected behavior wasattributed to intramolecular folding of the rotaxanes, as indicated by extensive theoretical calculations.This evidences the importance to take into account the conformational flexibility of large molecularstructures when designing functional switchable systems.Fil: Riebe, Jan. Universitat Essen; AlemaniaFil: Bädorf, Benedikt. Universitat Bonn; AlemaniaFil: Löffelsender, Sarah. Universitat Bonn; AlemaniaFil: Gutierrez Suburu, Matias Ezequiel. Universität Münster; AlemaniaFil: Rivas Aiello, Maria Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Strassert, Cristian A.. Universität Münster; AlemaniaFil: Grimme, Stefan. Universitat Bonn; AlemaniaFil: Niemeyer, Jochen. Universitat Essen; AlemaniaNature2024-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/263581Riebe, Jan; Bädorf, Benedikt; Löffelsender, Sarah; Gutierrez Suburu, Matias Ezequiel; Rivas Aiello, Maria Belen; et al.; Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes; Nature; Communications Chemistry; 7; 1; 8-2024; 1-112399-3669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.nature.com/articles/s42004-024-01247-7info:eu-repo/semantics/altIdentifier/doi/10.1038/s42004-024-01247-7info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:59:30Zoai:ri.conicet.gov.ar:11336/263581instacron: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:34982025-09-03 09:59:30.47CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes
title Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes
spellingShingle Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes
Riebe, Jan
ROTAXANES
SINGLET OXYGEN
PORPHYRIN
title_short Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes
title_full Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes
title_fullStr Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes
title_full_unstemmed Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes
title_sort Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes
dc.creator.none.fl_str_mv Riebe, Jan
Bädorf, Benedikt
Löffelsender, Sarah
Gutierrez Suburu, Matias Ezequiel
Rivas Aiello, Maria Belen
Strassert, Cristian A.
Grimme, Stefan
Niemeyer, Jochen
author Riebe, Jan
author_facet Riebe, Jan
Bädorf, Benedikt
Löffelsender, Sarah
Gutierrez Suburu, Matias Ezequiel
Rivas Aiello, Maria Belen
Strassert, Cristian A.
Grimme, Stefan
Niemeyer, Jochen
author_role author
author2 Bädorf, Benedikt
Löffelsender, Sarah
Gutierrez Suburu, Matias Ezequiel
Rivas Aiello, Maria Belen
Strassert, Cristian A.
Grimme, Stefan
Niemeyer, Jochen
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv ROTAXANES
SINGLET OXYGEN
PORPHYRIN
topic ROTAXANES
SINGLET OXYGEN
PORPHYRIN
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Rotaxanes are mechanically interlocked molecules where a ring (macrocycle) is threaded onto a linearmolecule (thread). The position of the macrocycle on different stations on the thread can be controlledin response to external stimuli, making rotaxanes applicable as molecular switches. Here we show that bistable rotaxanes based on the combination of a Zn(II) tetraphenylporphyrin photosensitizer,attached to the macrocycle, and a black-hole-quencher, attached to the thread, are capable of singletoxygen production which can be switched on/off by the addition of base/acid. However, we found thatonly a sufficiently long linker between both stations on the thread enabled switchability, and that thedirection of switching was inversed with regard to the original design. This unexpected behavior wasattributed to intramolecular folding of the rotaxanes, as indicated by extensive theoretical calculations.This evidences the importance to take into account the conformational flexibility of large molecularstructures when designing functional switchable systems.
Fil: Riebe, Jan. Universitat Essen; Alemania
Fil: Bädorf, Benedikt. Universitat Bonn; Alemania
Fil: Löffelsender, Sarah. Universitat Bonn; Alemania
Fil: Gutierrez Suburu, Matias Ezequiel. Universität Münster; Alemania
Fil: Rivas Aiello, Maria Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Strassert, Cristian A.. Universität Münster; Alemania
Fil: Grimme, Stefan. Universitat Bonn; Alemania
Fil: Niemeyer, Jochen. Universitat Essen; Alemania
description Rotaxanes are mechanically interlocked molecules where a ring (macrocycle) is threaded onto a linearmolecule (thread). The position of the macrocycle on different stations on the thread can be controlledin response to external stimuli, making rotaxanes applicable as molecular switches. Here we show that bistable rotaxanes based on the combination of a Zn(II) tetraphenylporphyrin photosensitizer,attached to the macrocycle, and a black-hole-quencher, attached to the thread, are capable of singletoxygen production which can be switched on/off by the addition of base/acid. However, we found thatonly a sufficiently long linker between both stations on the thread enabled switchability, and that thedirection of switching was inversed with regard to the original design. This unexpected behavior wasattributed to intramolecular folding of the rotaxanes, as indicated by extensive theoretical calculations.This evidences the importance to take into account the conformational flexibility of large molecularstructures when designing functional switchable systems.
publishDate 2024
dc.date.none.fl_str_mv 2024-08
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/11336/263581
Riebe, Jan; Bädorf, Benedikt; Löffelsender, Sarah; Gutierrez Suburu, Matias Ezequiel; Rivas Aiello, Maria Belen; et al.; Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes; Nature; Communications Chemistry; 7; 1; 8-2024; 1-11
2399-3669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/263581
identifier_str_mv Riebe, Jan; Bädorf, Benedikt; Löffelsender, Sarah; Gutierrez Suburu, Matias Ezequiel; Rivas Aiello, Maria Belen; et al.; Molecular folding governs switchable singlet oxygen photoproduction in porphyrin-decorated bistable rotaxanes; Nature; Communications Chemistry; 7; 1; 8-2024; 1-11
2399-3669
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://www.nature.com/articles/s42004-024-01247-7
info:eu-repo/semantics/altIdentifier/doi/10.1038/s42004-024-01247-7
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 Nature
publisher.none.fl_str_mv Nature
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 13.13397

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