Solid-state NMR spectroscopy proves the presence of penta-coordinated Sc sites in MIL-100(Sc)

Raynald Giovine; Christophe Volkringer; Sharon E. Ashbrook; Julien Trébosc; David McKay; Thierry Loiseau; Jean-Paul Amoureux; Olivier Lafon; Frédérique Pourpoint

doi:10.1002/chem.201700584

Solid-state NMR spectroscopy proves the presence of penta-coordinated Sc sites in MIL-100(Sc)

Raynald Giovine, Christophe Volkringer, Sharon E. Ashbrook, Julien Trébosc, David McKay, Thierry Loiseau, Jean-Paul Amoureux, Olivier Lafon, Frédérique Pourpoint

Research output: Contribution to journal › Article › peer-review

Abstract

Advanced solid-state NMR methods and first-principles calculations demonstrate for the first time the formation of penta-coordinated scandium sites. These coordinatively unsaturated sites were shown during the thermal activation of scandium-based metal-organic frameworks (MOFs). A ⁴⁵Sc NMR experiment allows their specific observation in activated Sc₃BTB₂ (H₃BTB=1,3,5-tris(4-carboxyphenyl)benzene) and MIL-100(Sc) MOFs. The assignment of the ScO₅ groups is supported by the DFT calculations of NMR parameters. The presence of ScO₅ Lewis acid sites in MIL-100(Sc) explains furthermore its catalytic activity. The first NMR experiment to probe ¹³C−⁴⁵Sc distances is also introduced. This advanced solid-state NMR pulse sequence allows the demonstration of the shrinkage of the MIL-100(Sc) network when the activation temperature is raised.

Original language	English
Pages (from-to)	9525-9534
Journal	Chemistry - A European Journal
Volume	23
Issue number	40
Early online date	24 May 2017
DOIs	https://doi.org/10.1002/chem.201700584
Publication status	Published - 18 Jul 2017

Keywords

Density functional calculations
Metal–organic frameworks
MIL-100(Sc)
ScO5
13C−45Sc

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10.1002/chem.201700584

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© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1002/chem.201700584
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title = "Solid-state NMR spectroscopy proves the presence of penta-coordinated Sc sites in MIL-100(Sc)",

abstract = "Advanced solid-state NMR methods and first-principles calculations demonstrate for the first time the formation of penta-coordinated scandium sites. These coordinatively unsaturated sites were shown during the thermal activation of scandium-based metal-organic frameworks (MOFs). A 45Sc NMR experiment allows their specific observation in activated Sc3BTB2 (H3BTB=1,3,5-tris(4-carboxyphenyl)benzene) and MIL-100(Sc) MOFs. The assignment of the ScO5 groups is supported by the DFT calculations of NMR parameters. The presence of ScO5 Lewis acid sites in MIL-100(Sc) explains furthermore its catalytic activity. The first NMR experiment to probe 13C−45Sc distances is also introduced. This advanced solid-state NMR pulse sequence allows the demonstration of the shrinkage of the MIL-100(Sc) network when the activation temperature is raised.",

keywords = "Density functional calculations, Metal–organic frameworks, MIL-100(Sc), ScO5, 13C−45Sc",

author = "Raynald Giovine and Christophe Volkringer and Ashbrook, {Sharon E.} and Julien Tr{\'e}bosc and David McKay and Thierry Loiseau and Jean-Paul Amoureux and Olivier Lafon and Fr{\'e}d{\'e}rique Pourpoint",

note = "Chevreul Institute (FR 2638), Minist{\`e}re de l′Enseignement Sup{\'e}rieur et de la Recherche, R{\'e}gion Hauts-de-France, and FEDER are acknowledged for supporting and partially funding this work. Authors are also grateful for funding supported by contract ANR-14-CE07-0009-01. ",

year = "2017",

month = jul,

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doi = "10.1002/chem.201700584",

language = "English",

volume = "23",

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journal = "Chemistry - A European Journal",

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publisher = "John Wiley & Sons, Ltd",

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T1 - Solid-state NMR spectroscopy proves the presence of penta-coordinated Sc sites in MIL-100(Sc)

AU - Giovine, Raynald

AU - Volkringer, Christophe

AU - Ashbrook, Sharon E.

AU - Trébosc, Julien

AU - McKay, David

AU - Loiseau, Thierry

AU - Amoureux, Jean-Paul

AU - Lafon, Olivier

AU - Pourpoint, Frédérique

N1 - Chevreul Institute (FR 2638), Ministère de l′Enseignement Supérieur et de la Recherche, Région Hauts-de-France, and FEDER are acknowledged for supporting and partially funding this work. Authors are also grateful for funding supported by contract ANR-14-CE07-0009-01.

PY - 2017/7/18

Y1 - 2017/7/18

N2 - Advanced solid-state NMR methods and first-principles calculations demonstrate for the first time the formation of penta-coordinated scandium sites. These coordinatively unsaturated sites were shown during the thermal activation of scandium-based metal-organic frameworks (MOFs). A 45Sc NMR experiment allows their specific observation in activated Sc3BTB2 (H3BTB=1,3,5-tris(4-carboxyphenyl)benzene) and MIL-100(Sc) MOFs. The assignment of the ScO5 groups is supported by the DFT calculations of NMR parameters. The presence of ScO5 Lewis acid sites in MIL-100(Sc) explains furthermore its catalytic activity. The first NMR experiment to probe 13C−45Sc distances is also introduced. This advanced solid-state NMR pulse sequence allows the demonstration of the shrinkage of the MIL-100(Sc) network when the activation temperature is raised.

AB - Advanced solid-state NMR methods and first-principles calculations demonstrate for the first time the formation of penta-coordinated scandium sites. These coordinatively unsaturated sites were shown during the thermal activation of scandium-based metal-organic frameworks (MOFs). A 45Sc NMR experiment allows their specific observation in activated Sc3BTB2 (H3BTB=1,3,5-tris(4-carboxyphenyl)benzene) and MIL-100(Sc) MOFs. The assignment of the ScO5 groups is supported by the DFT calculations of NMR parameters. The presence of ScO5 Lewis acid sites in MIL-100(Sc) explains furthermore its catalytic activity. The first NMR experiment to probe 13C−45Sc distances is also introduced. This advanced solid-state NMR pulse sequence allows the demonstration of the shrinkage of the MIL-100(Sc) network when the activation temperature is raised.

KW - Density functional calculations

KW - Metal–organic frameworks

KW - MIL-100(Sc)

KW - ScO5

KW - 13C−45Sc

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U2 - 10.1002/chem.201700584

DO - 10.1002/chem.201700584

M3 - Article

SN - 1521-3765

VL - 23

SP - 9525

EP - 9534

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 40

ER -

Solid-state NMR spectroscopy proves the presence of penta-coordinated Sc sites in MIL-100(Sc)

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