Local Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence Spectroscopies
Grafting molecular precursors on partially dehydroxylated silica followed by a thermal treatment yields silica-supported M(III) sites for a broad range of metals. They display unique properties such as high activity in olefin polymerization and alkane dehydrogenation (M = Cr) or efficient luminescen...
- Autores:
- Tipo de recurso:
- Fecha de publicación:
- 2017
- Institución:
- Universidad de Medellín
- Repositorio:
- Repositorio UDEM
- Idioma:
- eng
- OAI Identifier:
- oai:repository.udem.edu.co:11407/4261
- Acceso en línea:
- http://hdl.handle.net/11407/4261
- Palabra clave:
- Amides
Chromium compounds
Ethylene
Ligands
Luminescence
Nitrogen
Nuclear magnetic resonance spectroscopy
Polymerization
Silica
Spectroscopy
Structural properties
Surface properties
Ytterbium
Alkane dehydrogenations
Chemical and physical properties
Dynamic nuclear polarization
Luminescence properties
Luminescence spectroscopy
Non-radiative deactivation
Photophysical properties
Spectroscopic technique
Electron spin resonance spectroscopy
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| dc.title.spa.fl_str_mv |
Local Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence Spectroscopies |
| title |
Local Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence Spectroscopies |
| spellingShingle |
Local Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence Spectroscopies Amides Chromium compounds Ethylene Ligands Luminescence Nitrogen Nuclear magnetic resonance spectroscopy Polymerization Silica Spectroscopy Structural properties Surface properties Ytterbium Alkane dehydrogenations Chemical and physical properties Dynamic nuclear polarization Luminescence properties Luminescence spectroscopy Non-radiative deactivation Photophysical properties Spectroscopic technique Electron spin resonance spectroscopy |
| title_short |
Local Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence Spectroscopies |
| title_full |
Local Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence Spectroscopies |
| title_fullStr |
Local Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence Spectroscopies |
| title_full_unstemmed |
Local Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence Spectroscopies |
| title_sort |
Local Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence Spectroscopies |
| dc.contributor.affiliation.spa.fl_str_mv |
Delley, M.F., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, Switzerland Lapadula, G., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, Switzerland Núñez-Zarur, F., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, Switzerland, Facultad de Facultad de Ciencias Básicas, Universidad de Medellín, Carrera 87 N 30-65, Medellín, Colombia Comas-Vives, A., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, Switzerland Kalendra, V., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, Switzerland, Faculty of Physics, Vilnius University, Sauletekio 9, Vilnius, Lithuania Jeschke, G., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, Switzerland Baabe, D., Institut für Anorganische und Analytische Chemie, TU Braunschweig, Hagenring 30, Braunschweig, Germany Walter, M.D., Institut für Anorganische und Analytische Chemie, TU Braunschweig, Hagenring 30, Braunschweig, Germany Rossini, A.J., Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland Lesage, A., Centre de RMN À Tres Hauts Champs, Institut de Sciences Analytiques, Université de Lyon (CNRS/ENS Lyon/UCB Lyon 1), Villeurbanne, France Emsley, L., Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland Maury, O., Laboratoire de Chimie de l'Ens Lyon, Université de Lyon (CNRS/ENS Lyon/UCB LyonUMR 5182), 46 alleé d'Italie, Lyon, France Copéret, C., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, Switzerland |
| dc.subject.keyword.eng.fl_str_mv |
Amides Chromium compounds Ethylene Ligands Luminescence Nitrogen Nuclear magnetic resonance spectroscopy Polymerization Silica Spectroscopy Structural properties Surface properties Ytterbium Alkane dehydrogenations Chemical and physical properties Dynamic nuclear polarization Luminescence properties Luminescence spectroscopy Non-radiative deactivation Photophysical properties Spectroscopic technique Electron spin resonance spectroscopy |
| topic |
Amides Chromium compounds Ethylene Ligands Luminescence Nitrogen Nuclear magnetic resonance spectroscopy Polymerization Silica Spectroscopy Structural properties Surface properties Ytterbium Alkane dehydrogenations Chemical and physical properties Dynamic nuclear polarization Luminescence properties Luminescence spectroscopy Non-radiative deactivation Photophysical properties Spectroscopic technique Electron spin resonance spectroscopy |
| description |
Grafting molecular precursors on partially dehydroxylated silica followed by a thermal treatment yields silica-supported M(III) sites for a broad range of metals. They display unique properties such as high activity in olefin polymerization and alkane dehydrogenation (M = Cr) or efficient luminescence properties (M = Yb and Eu) essential for bioimaging. Here, we interrogate the local structure of the M(III) surface sites obtained from two molecular precursors, amides M(N(SiMe3)2)3 vs siloxides (M(OSi(OtBu)3)3·L with L = (THF)2 or HOSi(OtBu)3 for M = Cr, Yb, Eu, and Y, by a combination of advanced spectroscopic techniques (EPR, IR, XAS, UV-vis, NMR, luminescence spectroscopies). For paramagnetic Cr(III), EPR (HYSCORE) spectroscopy shows hyperfine coupling to nitrogen only when the amide precursor is used, consistent with the presence of nitrogen neighbors. This changes their specific reactivity compared to Cr(III) sites in oxygen environments obtained from siloxide precursors: no coordination of CO and oligomer formation during the polymerization of ethylene due to the presence of a N-donor ligand. The presence of the N-ligand also affects the photophysical properties of Yb and Eu by decreasing their lifetime, probably due to nonradiative deactivation of excited states by N-H bonds. Both types of precursors lead to a distribution of surface sites according to reactivity for Cr, luminescence spectroscopy for Yb and Eu, and dynamic nuclear polarization surface-enhanced 89Y NMR spectroscopy (DNP SENS). In particular, DNP SENS provides molecular-level information about the structure of surface sites by evidencing the presence of tri-, tetra-, and pentacoordinated Y-surface sites. This study provides unprecedented evidence and tools to assess the local structure of metal surface sites in relation to their chemical and physical properties. © 2017 American Chemical Society. |
| publishDate |
2017 |
| dc.date.accessioned.none.fl_str_mv |
2017-12-19T19:36:42Z |
| dc.date.available.none.fl_str_mv |
2017-12-19T19:36:42Z |
| dc.date.created.none.fl_str_mv |
2017 |
| dc.type.eng.fl_str_mv |
Article |
| dc.type.coarversion.fl_str_mv |
http://purl.org/coar/version/c_970fb48d4fbd8a85 |
| dc.type.coar.fl_str_mv |
http://purl.org/coar/resource_type/c_6501 http://purl.org/coar/resource_type/c_2df8fbb1 |
| dc.type.driver.none.fl_str_mv |
info:eu-repo/semantics/article |
| dc.identifier.issn.none.fl_str_mv |
27863 |
| dc.identifier.uri.none.fl_str_mv |
http://hdl.handle.net/11407/4261 |
| dc.identifier.doi.none.fl_str_mv |
10.1021/jacs.7b02179 |
| dc.identifier.reponame.spa.fl_str_mv |
reponame:Repositorio Institucional Universidad de Medellín |
| dc.identifier.instname.spa.fl_str_mv |
instname:Universidad de Medellín |
| identifier_str_mv |
27863 10.1021/jacs.7b02179 reponame:Repositorio Institucional Universidad de Medellín instname:Universidad de Medellín |
| url |
http://hdl.handle.net/11407/4261 |
| dc.language.iso.none.fl_str_mv |
eng |
| language |
eng |
| dc.relation.isversionof.spa.fl_str_mv |
https://www.scopus.com/inward/record.uri?eid=2-s2.0-85021997782&doi=10.1021%2fjacs.7b02179&partnerID=40&md5=87369cc3927c18a3b47e476d8ee2231b |
| dc.relation.ispartofes.spa.fl_str_mv |
Journal of the American Chemical Society Journal of the American Chemical Society Volume 139, Issue 26, 5 July 2017, Pages 8855-8867 |
| dc.relation.references.spa.fl_str_mv |
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http://purl.org/coar/access_right/c_16ec |
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American Chemical Society |
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Facultad de Ciencias Básicas |
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Scopus |
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Universidad de Medellín |
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Repositorio Institucional Universidad de Medellin |
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2017-12-19T19:36:42Z2017-12-19T19:36:42Z201727863http://hdl.handle.net/11407/426110.1021/jacs.7b02179reponame:Repositorio Institucional Universidad de Medellíninstname:Universidad de MedellínGrafting molecular precursors on partially dehydroxylated silica followed by a thermal treatment yields silica-supported M(III) sites for a broad range of metals. They display unique properties such as high activity in olefin polymerization and alkane dehydrogenation (M = Cr) or efficient luminescence properties (M = Yb and Eu) essential for bioimaging. Here, we interrogate the local structure of the M(III) surface sites obtained from two molecular precursors, amides M(N(SiMe3)2)3 vs siloxides (M(OSi(OtBu)3)3·L with L = (THF)2 or HOSi(OtBu)3 for M = Cr, Yb, Eu, and Y, by a combination of advanced spectroscopic techniques (EPR, IR, XAS, UV-vis, NMR, luminescence spectroscopies). For paramagnetic Cr(III), EPR (HYSCORE) spectroscopy shows hyperfine coupling to nitrogen only when the amide precursor is used, consistent with the presence of nitrogen neighbors. This changes their specific reactivity compared to Cr(III) sites in oxygen environments obtained from siloxide precursors: no coordination of CO and oligomer formation during the polymerization of ethylene due to the presence of a N-donor ligand. The presence of the N-ligand also affects the photophysical properties of Yb and Eu by decreasing their lifetime, probably due to nonradiative deactivation of excited states by N-H bonds. Both types of precursors lead to a distribution of surface sites according to reactivity for Cr, luminescence spectroscopy for Yb and Eu, and dynamic nuclear polarization surface-enhanced 89Y NMR spectroscopy (DNP SENS). In particular, DNP SENS provides molecular-level information about the structure of surface sites by evidencing the presence of tri-, tetra-, and pentacoordinated Y-surface sites. This study provides unprecedented evidence and tools to assess the local structure of metal surface sites in relation to their chemical and physical properties. © 2017 American Chemical Society.engAmerican Chemical SocietyFacultad de Ciencias Básicashttps://www.scopus.com/inward/record.uri?eid=2-s2.0-85021997782&doi=10.1021%2fjacs.7b02179&partnerID=40&md5=87369cc3927c18a3b47e476d8ee2231bJournal of the American Chemical SocietyJournal of the American Chemical Society Volume 139, Issue 26, 5 July 2017, Pages 8855-8867Allouche, F., Lapadula, G., Siddiqi, G., Lukens, W. W., Maury, O., Le Guennic, B., . . . Copéret, C. (2017). Magnetic memory from site isolated dy(III) on silica materials. ACS Central Science, 3(3), 244-249. doi:10.1021/acscentsci.7b00035Alyea, E. C., Bradley, D. C., Copperthwaite, R. 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Accounts of Chemical Research, 45(2), 206-214. doi:10.1021/ar2001342ScopusLocal Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence SpectroscopiesArticleinfo:eu-repo/semantics/articlehttp://purl.org/coar/version/c_970fb48d4fbd8a85http://purl.org/coar/resource_type/c_6501http://purl.org/coar/resource_type/c_2df8fbb1Delley, M.F., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, SwitzerlandLapadula, G., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, SwitzerlandNúñez-Zarur, F., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, Switzerland, Facultad de Facultad de Ciencias Básicas, Universidad de Medellín, Carrera 87 N 30-65, Medellín, ColombiaComas-Vives, A., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, SwitzerlandKalendra, V., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, Switzerland, Faculty of Physics, Vilnius University, Sauletekio 9, Vilnius, LithuaniaJeschke, G., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, SwitzerlandBaabe, D., Institut für Anorganische und Analytische Chemie, TU Braunschweig, Hagenring 30, Braunschweig, GermanyWalter, M.D., Institut für Anorganische und Analytische Chemie, TU Braunschweig, Hagenring 30, Braunschweig, GermanyRossini, A.J., Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, SwitzerlandLesage, A., Centre de RMN À Tres Hauts Champs, Institut de Sciences Analytiques, Université de Lyon (CNRS/ENS Lyon/UCB Lyon 1), Villeurbanne, FranceEmsley, L., Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, SwitzerlandMaury, O., Laboratoire de Chimie de l'Ens Lyon, Université de Lyon (CNRS/ENS Lyon/UCB LyonUMR 5182), 46 alleé d'Italie, Lyon, FranceCopéret, C., Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, SwitzerlandDelley M.F.Lapadula G.Núñez-Zarur F.Comas-Vives A.Kalendra V.Jeschke G.Baabe D.Walter M.D.Rossini A.J.Lesage A.Emsley L.Maury O.Copéret C.Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1-5, Zürich, SwitzerlandFacultad de Facultad de Ciencias Básicas, Universidad de Medellín, Carrera 87 N 30-65, Medellín, ColombiaFaculty of Physics, Vilnius University, Sauletekio 9, Vilnius, LithuaniaInstitut für Anorganische und Analytische Chemie, TU Braunschweig, Hagenring 30, Braunschweig, GermanyInstitut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, SwitzerlandCentre de RMN À Tres Hauts Champs, Institut de Sciences Analytiques, Université de Lyon (CNRS/ENS Lyon/UCB Lyon 1), Villeurbanne, FranceLaboratoire de Chimie de l'Ens Lyon, Université de Lyon (CNRS/ENS Lyon/UCB LyonUMR 5182), 46 alleé d'Italie, Lyon, FranceAmidesChromium compoundsEthyleneLigandsLuminescenceNitrogenNuclear magnetic resonance spectroscopyPolymerizationSilicaSpectroscopyStructural propertiesSurface propertiesYtterbiumAlkane dehydrogenationsChemical and physical propertiesDynamic nuclear polarizationLuminescence propertiesLuminescence spectroscopyNon-radiative deactivationPhotophysical propertiesSpectroscopic techniqueElectron spin resonance spectroscopyGrafting molecular precursors on partially dehydroxylated silica followed by a thermal treatment yields silica-supported M(III) sites for a broad range of metals. They display unique properties such as high activity in olefin polymerization and alkane dehydrogenation (M = Cr) or efficient luminescence properties (M = Yb and Eu) essential for bioimaging. Here, we interrogate the local structure of the M(III) surface sites obtained from two molecular precursors, amides M(N(SiMe3)2)3 vs siloxides (M(OSi(OtBu)3)3·L with L = (THF)2 or HOSi(OtBu)3 for M = Cr, Yb, Eu, and Y, by a combination of advanced spectroscopic techniques (EPR, IR, XAS, UV-vis, NMR, luminescence spectroscopies). For paramagnetic Cr(III), EPR (HYSCORE) spectroscopy shows hyperfine coupling to nitrogen only when the amide precursor is used, consistent with the presence of nitrogen neighbors. This changes their specific reactivity compared to Cr(III) sites in oxygen environments obtained from siloxide precursors: no coordination of CO and oligomer formation during the polymerization of ethylene due to the presence of a N-donor ligand. The presence of the N-ligand also affects the photophysical properties of Yb and Eu by decreasing their lifetime, probably due to nonradiative deactivation of excited states by N-H bonds. Both types of precursors lead to a distribution of surface sites according to reactivity for Cr, luminescence spectroscopy for Yb and Eu, and dynamic nuclear polarization surface-enhanced 89Y NMR spectroscopy (DNP SENS). In particular, DNP SENS provides molecular-level information about the structure of surface sites by evidencing the presence of tri-, tetra-, and pentacoordinated Y-surface sites. This study provides unprecedented evidence and tools to assess the local structure of metal surface sites in relation to their chemical and physical properties. © 2017 American Chemical Society.http://purl.org/coar/access_right/c_16ec11407/4261oai:repository.udem.edu.co:11407/42612020-05-27 18:29:00.631Repositorio Institucional Universidad de Medellinrepositorio@udem.edu.co |