NMR Crystallography

© Owned by the authors, published by EDP Sciences, 2012

This is an Open Access article distributed under the terms of the Creative Commons Attribution License 2.0, which

Organized by

Thibault Charpentier [email protected]

Patrick Berthault

[email protected]

Constantin Meis

[email protected]

Experiment and Modelling in Structural NMR

November 28th – December 2

nd

₂₀₁₁

INSTN – CEA Saclay, France

Charlotte Martineau

Institut Lavoisier de Versailles

France

NMR Crystallography

[02003]

C. Martineau & F. Taulelle

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Lorsque certaines causes produisent certains effets, les éléments de symétrie des causes doivent se retrouver dans les effets produits.

Lorsque certains effets révèlent une certaine dissymétrie, cette dysymmétrie doit se retrouver dans les causes qui leur ont donnée naissance.

La réciproque de ces deux propositions n’est pas vraie, au moins pratiquement, c’est-à-dire que les effets produits peuvent être plus symétriques que les causes.

C. Martineau & F. Taulelle

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Unit Cell: Metrics & Nature of the Atoms

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Unit Cell Parameters

Space Group

Unit Cell content

Integrant Unit

Refinement

Structural Model

Structure

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Unit Cell Parameters

Space Group

Unit Cell content

Integrant Unit

Refinement

Structural Model

Structure

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Unit Cell Parameters

Space Group

Unit Cell content

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Refinement

Structural Model

Structure

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Unit Cell Parameters

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27_{Al frequency (ppm)} -100 -50 0 50 Exp. Rec. 1 2

B0 = 11.7 T MAS 30 kHz

19_{F frequency (ppm)}

-200 -160 -120 -80 -40 0 40 Exp. Rec. 1 2 5 6 7 8

B₀ = 7 T

MAS 54 kHz

(38 eq)



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C. Martineau & F. Taulelle

27_{Al frequency (ppm)}

-100 -50 0 50 Exp. Rec. 1 2

B0 = 11.7 T MAS 30 kHz

19_{F frequency (ppm)}

-200 -160 -120 -80 -40 0 40 Exp. Rec. 1 2 3 4 5 6 7 8

B0 = 7 T MAS 54 kHz

(38 eq)



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Unit Cell Parameters

Space Group

Unit Cell content

Integrant Unit

Refinement

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Structure



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Exp.

Rec.

Al1

B0 = 11.7 T

Al2

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27_{Al frequency (ppm)}

-100 -50

0 50 Exp.

Rec.

400 300 200 100 0 -100 -200 -300 -400

27_{Al frequency (kHz)}

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C. Martineau & F. Taulelle

19_{F frequency (ppm)}

-200 -160 -120 -80 -40 0

40 Exp.

Rec.

1 2 3 4 5

6 7 8

SPD

F6

F5 F4

F2 F1 F3

F8 F7

-150 -100 -50 0 50

-150 -100 -50 0 50

Exp. 19_{F isotropic chemical shift (ppm)}

Calc.

19

F isotropic chemical shift (ppm)

= - 0.83

-17.6, with R

_{= 0.999}

Zheng et al., J. Phys. Chem. C 113 (2009) 15018

B₀ = 7 T, MAS 54 kHz

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21

19_{F frequency (ppm)} -200 -160 -120 -80 -40 0 40 Exp. Rec. 1 2 3 4 5 6 7 8 SPD DFT F6 F6

F5 F4

F5 F4

F2,F1 F3 F2 F1 F3

F8 F7

F8 F7

B0 = 7 T, MAS 54 kHz

-150 -100 -50 0 50

Exp. 19_{F isotropic chemical shift (ppm)}

Calc.

19F isotropic chemical shift (ppm)

= - 0.83

-17.6, with R

= 0.999



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Zheng et al., J. Phys. Chem. C 113 (2009) 15018

22

C. Martineau & F. Taulelle

23

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Unit Cell Parameters

Space Group

Unit Cell content

Integrant Unit

Refinement

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Structural Model

Structure

19_{F SQ dimension (ppm)} -180 -160 -140 -120 -100 -80 -60 -40 -20 0 20

F5 F4

F2

F3

F1

T = 28°C T = 93°C

T = 89°C

T = 81°C

T = 72°C

T = 64°C

T = 56°C

T = 48°C

T = 40°C

T = 32°C

F6

F8

F7

B

F1

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24 C. Martineau & F. Taulelle

F6

F1 F8 F7

F6 _{F5 F4}

F2,F1 F3

F8 F7

B -160 -120 -80 -40 0 -160 -120 -80 -40 0 -160 -120 -80 -40 0 -160 -120 -80 -40 0

19_{F frequency (ppm)} 19_{F frequency (ppm)}

19

F frequency (ppm)

19F frequency (ppm)

19_{F SQ dimension (ppm)} -160 -120 -80 -40 0 -160 -120 -80 -40 0 19

F SQ dimension (ppm)

F6

F1 F8 F7

-160 -120 -80 -40 0 -160 -120 -80 -40 0

19_{F SQ dimension (ppm)}

19

F SQ dimension (ppm)

F6 F5 F4

F2,F1 F3

F8 F7

B

T = 28ºC

T = 90ºC

B0 = 7 T, MAS 54 kHz

25

F6

_{F5 F4}

F2,

F1

F3

F8 F7

-160

-120

-80

-40

0

-160

-120

-80

-40

0

19

_{F frequency (ppm)}

F frequency (ppm)

B₀ = 7 T, MAS 54 kHz tmix = 2 ms

T = 28ºC

26

C. Martineau & F. Taulelle

19

_{F SQ dimension (ppm)}

-160

-120

-80

-40

0

-160

-120

-80

-40

0

F SQ dimension (ppm)

F6

F1

F8 F7

-160

-120

-80

-40

0

-160

-120

-80

-40

0

19

_{F SQ dimension (ppm)}

19

F SQ dimension (ppm)

F6

_{F5 F4}

F2,F1

F3

F8 F7

B

T = 28ºC

T = 90ºC

-160

0

27



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_{P dimension (ppm)}

-21

-18

-15

-12

-9

-6

-3

No dec.

1

_H/

_{Al dec.}

C. Martineau & F. Taulelle

- X-ray diffraction and

31

_{P MAS NMR spectrum}

_{‘Average’ Structural Model}

- Higher-resolution of the

31

_{P MAS NMR spectrum under multiple-resonance decoupling}

higher-resolution structural description

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