Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran
- Autores
- Siddiqui, Khalid M.; Bittmann, Simon F.; Hayes, Stuart A.; Krawczyk, Kamil M.; Sarracini, Antoine; Corthey, Gastón; Dsouza, Raison; Miller, R. J. Dwayne
- Año de publicación
- 2024
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- Isomerisation through stereochemical changes and modulation in bond order conjugation are processes that occur ubiquitously in diverse chemical systems and for photochromic spirocompounds, it imparts them their functionality as phototransformable molecules. However, these transformations have been notoriously challenging to observe in crystals due to steric hindrance but are necessary ingredients for the development of reversible spiro-based crystalline devices. Here, we report the detection of spectroscopic signatures of merocyanine due to photoisomerisation within crystalline spiropyran following 266 nm excitation. Our femtosecond spectroscopy experiments reveal bond breaking, isomerisation and increase in bond order conjugation towards the formation of merocynine on a sub-2 ps time scale. They further unveil a lifetime of several picoseconds for the initial open ring intermediate with subsequent relaxation to mercocyanine, with established back connversion pathways, which make the system highly reversible in the solid state. Supporting femtosecond electron diffraction studies suggest that lattice strain favours the return of photoproduct to the closed spiroform. Our work thus paves the way for novel ultrafast applications from spiropyran-derived compounds.
Fil: Siddiqui, Khalid M.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Bittmann, Simon F.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Hayes, Stuart A.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania
Fil: Krawczyk, Kamil M.. University of Toronto; Canadá
Fil: Sarracini, Antoine. University of Toronto; Canadá
Fil: Corthey, Gastón. Universidad Nacional de San Martin. Instituto de Nanosistemas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Dsouza, Raison. University of Toronto; Canadá
Fil: Miller, R. J. Dwayne. University of Toronto; Canadá - Materia
-
Spiropyran
Merocyanine
Photoisomerisation
Ultrafast spectroscopy - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
- Repositorio
.jpg)
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/261008
Ver los metadatos del registro completo
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Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyranSiddiqui, Khalid M.Bittmann, Simon F.Hayes, Stuart A.Krawczyk, Kamil M.Sarracini, AntoineCorthey, GastónDsouza, RaisonMiller, R. J. DwayneSpiropyranMerocyaninePhotoisomerisationUltrafast spectroscopyhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Isomerisation through stereochemical changes and modulation in bond order conjugation are processes that occur ubiquitously in diverse chemical systems and for photochromic spirocompounds, it imparts them their functionality as phototransformable molecules. However, these transformations have been notoriously challenging to observe in crystals due to steric hindrance but are necessary ingredients for the development of reversible spiro-based crystalline devices. Here, we report the detection of spectroscopic signatures of merocyanine due to photoisomerisation within crystalline spiropyran following 266 nm excitation. Our femtosecond spectroscopy experiments reveal bond breaking, isomerisation and increase in bond order conjugation towards the formation of merocynine on a sub-2 ps time scale. They further unveil a lifetime of several picoseconds for the initial open ring intermediate with subsequent relaxation to mercocyanine, with established back connversion pathways, which make the system highly reversible in the solid state. Supporting femtosecond electron diffraction studies suggest that lattice strain favours the return of photoproduct to the closed spiroform. Our work thus paves the way for novel ultrafast applications from spiropyran-derived compounds.Fil: Siddiqui, Khalid M.. Max Planck Institute for the Structure and Dynamics of Matter; AlemaniaFil: Bittmann, Simon F.. Max Planck Institute for the Structure and Dynamics of Matter; AlemaniaFil: Hayes, Stuart A.. Max Planck Institute for the Structure and Dynamics of Matter; AlemaniaFil: Krawczyk, Kamil M.. University of Toronto; CanadáFil: Sarracini, Antoine. University of Toronto; CanadáFil: Corthey, Gastón. Universidad Nacional de San Martin. Instituto de Nanosistemas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Dsouza, Raison. University of Toronto; CanadáFil: Miller, R. J. Dwayne. University of Toronto; CanadáSpringer2024-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/261008Siddiqui, Khalid M.; Bittmann, Simon F.; Hayes, Stuart A.; Krawczyk, Kamil M.; Sarracini, Antoine; et al.; Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran; Springer; Nature Communications; 15; 1; 12-2024; 1-82041-1723CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.nature.com/articles/s41467-024-54992-7info:eu-repo/semantics/altIdentifier/doi/10.1038/s41467-024-54992-7info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:07:42Zoai:ri.conicet.gov.ar:11336/261008instacron: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 10:07:42.577CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
| dc.title.none.fl_str_mv |
Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran |
| title |
Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran |
| spellingShingle |
Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran Siddiqui, Khalid M. Spiropyran Merocyanine Photoisomerisation Ultrafast spectroscopy |
| title_short |
Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran |
| title_full |
Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran |
| title_fullStr |
Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran |
| title_full_unstemmed |
Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran |
| title_sort |
Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran |
| dc.creator.none.fl_str_mv |
Siddiqui, Khalid M. Bittmann, Simon F. Hayes, Stuart A. Krawczyk, Kamil M. Sarracini, Antoine Corthey, Gastón Dsouza, Raison Miller, R. J. Dwayne |
| author |
Siddiqui, Khalid M. |
| author_facet |
Siddiqui, Khalid M. Bittmann, Simon F. Hayes, Stuart A. Krawczyk, Kamil M. Sarracini, Antoine Corthey, Gastón Dsouza, Raison Miller, R. J. Dwayne |
| author_role |
author |
| author2 |
Bittmann, Simon F. Hayes, Stuart A. Krawczyk, Kamil M. Sarracini, Antoine Corthey, Gastón Dsouza, Raison Miller, R. J. Dwayne |
| author2_role |
author author author author author author author |
| dc.subject.none.fl_str_mv |
Spiropyran Merocyanine Photoisomerisation Ultrafast spectroscopy |
| topic |
Spiropyran Merocyanine Photoisomerisation Ultrafast spectroscopy |
| purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| dc.description.none.fl_txt_mv |
Isomerisation through stereochemical changes and modulation in bond order conjugation are processes that occur ubiquitously in diverse chemical systems and for photochromic spirocompounds, it imparts them their functionality as phototransformable molecules. However, these transformations have been notoriously challenging to observe in crystals due to steric hindrance but are necessary ingredients for the development of reversible spiro-based crystalline devices. Here, we report the detection of spectroscopic signatures of merocyanine due to photoisomerisation within crystalline spiropyran following 266 nm excitation. Our femtosecond spectroscopy experiments reveal bond breaking, isomerisation and increase in bond order conjugation towards the formation of merocynine on a sub-2 ps time scale. They further unveil a lifetime of several picoseconds for the initial open ring intermediate with subsequent relaxation to mercocyanine, with established back connversion pathways, which make the system highly reversible in the solid state. Supporting femtosecond electron diffraction studies suggest that lattice strain favours the return of photoproduct to the closed spiroform. Our work thus paves the way for novel ultrafast applications from spiropyran-derived compounds. Fil: Siddiqui, Khalid M.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania Fil: Bittmann, Simon F.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania Fil: Hayes, Stuart A.. Max Planck Institute for the Structure and Dynamics of Matter; Alemania Fil: Krawczyk, Kamil M.. University of Toronto; Canadá Fil: Sarracini, Antoine. University of Toronto; Canadá Fil: Corthey, Gastón. Universidad Nacional de San Martin. Instituto de Nanosistemas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Dsouza, Raison. University of Toronto; Canadá Fil: Miller, R. J. Dwayne. University of Toronto; Canadá |
| description |
Isomerisation through stereochemical changes and modulation in bond order conjugation are processes that occur ubiquitously in diverse chemical systems and for photochromic spirocompounds, it imparts them their functionality as phototransformable molecules. However, these transformations have been notoriously challenging to observe in crystals due to steric hindrance but are necessary ingredients for the development of reversible spiro-based crystalline devices. Here, we report the detection of spectroscopic signatures of merocyanine due to photoisomerisation within crystalline spiropyran following 266 nm excitation. Our femtosecond spectroscopy experiments reveal bond breaking, isomerisation and increase in bond order conjugation towards the formation of merocynine on a sub-2 ps time scale. They further unveil a lifetime of several picoseconds for the initial open ring intermediate with subsequent relaxation to mercocyanine, with established back connversion pathways, which make the system highly reversible in the solid state. Supporting femtosecond electron diffraction studies suggest that lattice strain favours the return of photoproduct to the closed spiroform. Our work thus paves the way for novel ultrafast applications from spiropyran-derived compounds. |
| publishDate |
2024 |
| dc.date.none.fl_str_mv |
2024-12 |
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info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
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article |
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publishedVersion |
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http://hdl.handle.net/11336/261008 Siddiqui, Khalid M.; Bittmann, Simon F.; Hayes, Stuart A.; Krawczyk, Kamil M.; Sarracini, Antoine; et al.; Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran; Springer; Nature Communications; 15; 1; 12-2024; 1-8 2041-1723 CONICET Digital CONICET |
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http://hdl.handle.net/11336/261008 |
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Siddiqui, Khalid M.; Bittmann, Simon F.; Hayes, Stuart A.; Krawczyk, Kamil M.; Sarracini, Antoine; et al.; Ultrafast signatures of merocyanine overcoming steric impedance in crystalline spiropyran; Springer; Nature Communications; 15; 1; 12-2024; 1-8 2041-1723 CONICET Digital CONICET |
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eng |
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eng |
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Springer |
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Springer |
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dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
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