Techniques of solid-state NMR

EPJ Web of Conferences

30

, 02002 (2012)

DOI: 10.1051/epjconf/20123002002

© 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]

džƉĞƌŝŵĞŶƚ ĂŶĚDŽĚĞůůŝŶŐ ŝŶ^ƚƌƵĐƚƵƌĂůEDZ

EŽǀĞŵďĞƌ ϮϴƚŚʹ ĞĐĞŵďĞƌ Ϯ

ŶĚ

_ϮϬϭϭ

/E^dEʹ ^ĂĐůĂLJ͕&ƌĂŶĐĞ

Dominique Massiot

CEMHTI CNRS , France

Techniques of

Solid State NMR

[02002]

Techniques of solid

state NMR

Dominique Massiot

CEMHTI CNRS – TGIR-RMN-THC

Mostly focused on inorganic chemistry

•

 

Magic Angle Spinning

•

 

Quadrupolar nuclei

•

 

Excitation

•

 

MQMAS

•

 

Homo- and hetero- nuclear correlations D and J coupling

The different perturbating interactions

Q

2

Q

₁

Chemical Shift Anisotropy

electronic shielding

first shells, coordinence and

geometry

~10s of kHz

Dipolar interaction

neighboring spins

Distances

~kHz 1/r

3

Q

2

Q

₁

Indirect J Coupling

chemical bonding

Connectivity

Q

2

Q

₁

< 100s of Hz

I>1/2 up to MHz

Quadrupolar interaction

Electric Field Gradient

Surrounding Charges,

electrons and nuclei

geometry

Magic Angle Spinning

Static

-50 0

50 100

31

_{P Spin 1/2 CSA}

ω

α

A

zz

A

_xx

A

_yy

_β

x

y

z

Sum of crystallite

s spectra

Single Crystal rotation pattern

High-Resolution SS NMR

Static

MAS

Proton decoupling averages strong

31

_P-

1

_{H dipolar}

interaction

high speed MAS spinning attenuate dipolar

coupling

and modulates chemical shift anisotr

opy

Unresolved

CSA + Dipolaire

-50 -25 0 25 50 75 100 125

(ppm)

Resolved & Simplified

-50

-25 0 25 50 75 100 125

(ppm)

-50 -25 0 25 50 75 100 125

(ppm)

CSA + Dipolar

-50 -25 0 25 50 75 100 125

(ppm)

CSA + Dipolar

31

_P

I=1/2

D.Massiot "High Resolution Solid State NMR » in High Magnetic Fields: Applications in Condensed Matter Physics and Spectroscopy",

High-Resolution SS NMR

Static

-50 -25 0 25 50 75 100 125 (ppm) -50 -25 0 25 50 75 100 125 (ppm) -50 -25 0 25 50 75 100 125 (ppm)

MAS

Proton decoupling averages strong

31

_P-

1

_{H dipolar}

interaction

high speed MAS spinning attenuate dipolar

coupling

and modulates chemical shift anisotr

opy

Unresolved

CSA + Dipolaire

Resolved & Simplified

-50 -25 0 25 50 75 100 125 (ppm)

CSA + Dipolar

CSA + Dipolar

Slow MAS ~static

31

_P

I=1/2

D.Massiot "High Resolution Solid State NMR » in High Magnetic Fields: Applications in Condensed Matter Physics and Spectroscopy", LNP Vol 595, eds C. Berthier, L.P. Lévy, G. Martinez, Springer-Verlag, ISBN 3-540-43979-X 435-453 2002

Magic Angle Spinning – 1

st

_order

(

)

_∑

(

)

=

φ

+

ω

−

β

α

>

−

<

=

ν

+

θ

−

ν

+

ν

2

1

n

t

n

i

n

,

Q

2

0

1

m

,

m

C

A

e

r

2

)

m

2

1

(

Cos

P

First order

H

_I

<<

H

_z

MAS

54.74°

P

₂

(cos

θ

)

θ

0°

static

1

-0.5

90°

Dipolar

Chem. Shift

Quad 1st and 2nd

H

₀

D.Massiot "High Resolution Solid State NMR » in High Magnetic Fields: Applications in Condensed Matter Physics and Spectroscopy",

1st order MAS I=1/2 and I=1

Static

140kHz

2

_{H Plexiglass - static}

2

_{H Methiodine - MAS 3.5kHz}

-20

-10

0

10

20

30

31P single sited phosphate

30 kHz

6 kHz

60 kHz

High Resolution Hybrid materials

Zn

O

₃

P

C

₂

H

₄

C

O

₂

H

- 0.5 C

₆

H

₅

N

H

₂

Phosphonate (B.Bujoli – Nantes)

17

_{O I=5/2}

0.037% ab.

54 MHz

14

_{N I=1}

99.6 % ab.

29 MHz

67

_{Zn I=5/2}

4.11% ab.

25 MHz

13

_{P I=1/2}

100% ab.

162MHz

*

10 20 30 40

50 30

(ppm)

-100 -50 0 50 100 150

(ppm)

1

_{H I=1/2}

99.9% ab.

400MHz

13

_{C I=1/2}

1.18% ab.

100MHz

(ppm) 100 50 150

C

₆

H

₅

C

₂

H

₄

COOH

Homonuclear correlation

t

m

= 5 ms

t

_m

= 100 ms

6

4

2

0

6

4

2

0

(ppm)

6

4

2

0

(ppm)

Si-H (T

H

₎

Si-H (D

H

₎

Si-CH

3

(D

H

)

Si-H (D

H

₎

Si-CH

3

(D

H

)

Si-H (T

H

₎

φ1

φ2

0

1

-1

φ3

t1

mixing

t2

OH CH2 (EO)

CH (PO) CH2 (PO)

CH3-Si 0

1

0 100 400 900 1600 2500

τm½ / ms

( M – M0 ) / ( M - M0 )

Echo sélectif

+ échange

750 MHz

MAS 30 kHz

-1 0 1 2 3 4 5 6

~0 ms

δ (1H) / ppm

700 ms

200 ms

60 ms

10 ms

τm

τ

C

H

3

-Si

C

H

3

(PO)

C

H

₂

(PO)

C

H

(PO)

C

H

2

(EO)

-O

H

1

_H

1

_H

O

O

H

70 100

O

O

O

H

C

C H

H

₃

100

HO

O

Si

Si

S

O

S

O

O

O

CH

3

Si

Si

H

2

O

(EO)

(PO)

Hybrid Mesoporous

B. Alonso, P. Innocenzi, L. Malfatti, F. Fayon

Si

O

O

O

O

Q

Si

CH

3

O

O

O

T

Rapid Exchange

modéré

delayed

(PO)

(EO)

(EO)

Hierarchical materials

B.Alonso, F.Fayon, D.Massiot, H.Amenitsch, L.Malfatti, T.Kidchob, S.Costacurta, P.Innocenzi "Hybrid organic-inorganic mesostructured membranes: interfaces and organization at different length scales"

Organosilice - paires Thymine/Adenine

T-T

A-T

1

_{H DQ NMR}

750 MHz

33 kHz

Thymine : T

Adenine : A

G.Arrachart, C.Carcel, J.J.E.Moreau, G.Hartmeyer, B.Alonso, D.Massiot, G.Creff, J.L.Bantigniese, P.Dieudonnee, M.Wong Chi Man, G.Althoff, F.Babonneau,

C.Bonhomme

J. Mater. Chem.18 392-399 (2008)

NATURE CHEMISTRY | VOL 1 | APRIL 2009

Cationic order in LDH from

1

_{H NMR}

Powder XRD

c

10

20

30

40

50

60

2 (°)

O

A l

M g

A

n

-8.9 A

( 0 0 3 )

( 0 0 6 )

(11 0 )

Sample “

M g / A l - 2

Mg/Al = 2, A

n-

= NO

500

S.Cadars, G.Layrac, C.Gérardin, M.Deschamps, J.R.Yates, D.Tichit, D.Massiot

"Identification and Quantification of Defects in the Cation Ordering in Mg/Al Layered Double Hydroxides » Chem. Mater. 23 2821-2831 2011 M.Deschamps, F.Fayon, S.Cadars, A.-L.Rollet, D.Massiot

Chem. Chem. Phys. 13 8024 - 8030 2011

High Resolution Hybrid materials

Zn

O

₃

P

C

₂

H

₄

C

O

₂

H

- 0.5 C

₆

H

₅

N

H

₂

Phosphonate (B.Bujoli – Nantes)

17

_{O I=5/2}

0.037% ab.

54 MHz

14

_{N I=1}

99.6 % ab.

29 MHz

67

_{Zn I=5/2}

4.11% ab.

25 MHz

13

_{P I=1/2}

100% ab.

162MHz

*

10 20 30 40

50 30

(ppm)

-100 -50 0 50 100 150

(ppm)

1

_{H I=1/2}

99.9% ab.

400MHz

13

_{C I=1/2}

1.18% ab.

100MHz

(ppm) 100 50 150

C

₆

H

₅

C

₂

H

₄

COOH

D.Massiot, B.Alonso, F.Fayon, F.Fredoueil and B.Bujoli'New NMR developments for structural investigation of proton bearing materials at different length scales.'Solid State Sciences 311-16 (2001)

(ppm) 20

30

39.5Hz

42.5Hz

R {

14

_N}

13

_C

(ppm) 130 120 140

(ppm)

50 100

150

C

₆

H

₅

C

₂

H

₄

COOH

31

_P-

13

_C

1

_J

C

₂

H

₄

C

₆

H

₅

NH

₂

D.Massiot, F.Fayon, M.Deschamps, S.Cadars, P.Florian, V.Montouillout, N.Pellerin, J.Hiet, A.Rakhmatullin, C.Bessada‘ Detection and use of small J couplings in solid state NMR experiments.'

Comptes Rendus de Chimie 13 117-129 2010

13

_C

F.D.Sokolov, M.G.Babashkina, F.Fayon, A.I.Rakhmatullin, D.A.Safin, T.Pape, F.E.Hahn

"Novel Bicyclic Hexanuclear Copper(I) Aggregate. Structure and Solid State 31P CPMAS NMR Spectra of [(Cu3L3)2] and [Cu(PPh3)2L] Complexes of N-(diisopropoxythiophosphinyl)-N'-phenylthiourea (HL)"

J. Organomet. Chem. 694 167-172 2009

31_{P frequency (ppm)}

-20 0 20 40 60

N

J

₁

P-Cu 63 & 65 (I=3/2)

J

₂

P-P

-20 -10 0 10 Exp. Sim. 63

_Cu

65

_Cu

#1

63

_Cu

65

_Cu

#2

31

_P

I=1/2

A multi level system of transitions

2I+1 energy levels, 2I single quantum transitions

I=3/2

Zeeman

1

st

order

Quadrupolar

2

nd

order

Quadrupolar

ν

0

+ν

(1)Q

ν

0

ν

0

ν

0

ν

0

+ν

(1)Q

ν

0

3

ν

₀

+ν

(2) Q<m>

+ν

(2) Q<m>

+ν

(2) Q<m>

1

st

_{order quadrupolar interaction}

2

nd

_{order quadrupolar interaction}

( )

[

3

I

I

I

1

]

A

6

1

C

H

2

z

Q

20

Q

)

1

(

Q

=

−

+

( )

{

}

( )

{

}

⎥

⎥

_⎦

⎤

⎢

⎢

⎣

⎡

−

−

+

+

−

−

+

ω

=

−

−

1

I

2

1

I

I

2

A

A

1

I

8

1

I

I

4

A

A

2

C

H

2

z

Q

22

Q

2

2

2

z

Q

21

Q

1

2

0

2

Q

)

2

(

Q

Q

Zeeman

H

H

>>

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

α

β

η

−

−

β

ν

−

+

ν

=

ν

<

−

>

sin

cos

2

2

2

1

cos

3

)

m

2

1

(

2

1

2

2

Ti Based oxo-clusters –Ti

₁₆

O

₁₆

(OEt)

₃₂

200

400

600

800

(

ppm)

Solution

12,4 kHz

8,0 kHz

5,0 kHz

Solid

µ

₂

O

µ

4

O

µ

3

O

Ti

₁₆

O

₁₆

(OEt)

₃₂

4 µ

₂

-O / 8 µ

₃

-O / 4 µ

₄

-O

µ

2

O

µ

₄

O

Ti

µ

3

O

µ2 has strong chemical shift anisotropy

µ3 can have significant second order broadening

0 200 400 600

800

1000

1200 (ppm)

µ

2

O

µ

3

O

µ

4

O

Static

E. Scolan, C. Magnenet, D. Massiot and C. Sanchez'Surface and bulk characterisation of titanium oxo clusters and nanosized titania particles through 17O solid state NMR.'J. Mater. Chem. 92467-2474 (1999)

17

_O

I=5/2

2

nd

_{Order Quadrupolar interaction}

Second order Quadrupolar interaction

 

Second order effect implies a

shift of the

line (isotropic shift)

plus a shape.

 

All transitions

exhibit second order effects

 

Second order quadrupolar effects are scaled

by the principal field.

 

Usually

only central transition <-1/2,1/2>

can be seen for powdered samples.

η=0.0

η=1.0

η=0.8

η=0.6

η=0.4

η=0.2

-0.75

-0.5

-0.25

0

0.25

0.5

0.75

(MHz)

7 T

71

_Ga

11.7 T

71

_Ga

7 T

69

_Ga

(

α

β

γ

)

ν

+

ν

+

ν

=

ν

_<

_m

_,

_m

₋

₁

_>

₀

_<

iso

_m

(

_,

2

_m

)

₋

₁

_>

_<

(

2

_m

)

_,

_m

₋

₁

_>

,

,

Magic Angle Spinning -

2nd

_order

(

)

_∑

(

)

=

φ

+

ω

−

β

α

>

−

<

=

ν

+

θ

−

ν

+

ν

2

1

n

t

n

i

n

,

Q

2

0

1

m

,

m

C

A

e

r

2

)

m

2

1

(

Cos

P

First order

H

_I

<<

H

_z

P

4

(cos

θ

)

(

)

_∑

(

)

∑

₌

−

ω

+

φ

=

>

−

<

=

ν

+

θ

+

ν

4

1

n

t

n

i

)

2

(

n

4

,

2

,

0

l

l

)

2

(

l

l

I

,

m

0

1

m

,

m

C

B

P

Cos

A

e

r

Second order

H

I

<

H

z

MAS

54.74°

P

2

(cos

θ

)

θ

0°

static

1

-0.5

90°

H

₀

ppm

30.56°

90°

70.12°

0°=static

~MAS

Double Orientation Rotation - DOR

0 50 100 150 (ppm)

MAS

Static

Spin 5/2 -

quadrupolar

27

_{Al CaAl}

2

O

4

6 sites

0 50 100 150 (ppm)

DOR

P

4

(cos

θ

)

MAS

54.74°

P

2

(cos

θ

)

MAS Quadrupolar nuclei

-100

-50

0

50

100

(kHz)

0

76

(ppm)

750 MHz

600 MHz

500 MHz

400 MHz

300 MHz

200 MHz

27

_{Al in YAG two}

sites Al

_IV

and Al

_VI

Second order shift and width goes with

ν

_Q

²/

ν

₀

(Hz)

1D

2D TOP processing

D.Massiot, J.Hiet, N.Pellerin, F.Fayon, M.Deschamps, S.Steuernagel, P.J.Grandinetti "Two dimensional One Pulse MAS of Half-Integer Quadrupolar Nuclei"

27

_{Al in A9B2 (Al}

18

B

4

O

33

) 750 MHz

(Hz)

-450000 -300000

-150000 0

150000 300000

450000

Satellite transitions

Satellite transitions

Central transition

27

_{Al in A}

9

B

2

750 MHz - 15 kHz

27

_{Al in A9B2 (Al}

18

B

4

O

33

) from 7.0 up to 25 T

-100

-50

0

50

100

7.0 T

9.4 T

11.7 T

14.1 T

17.6 T

(ppm)

MAS

Resolution improves with H

₀²

NHMFL – Z. Gan

Gan, Gor’kov, Cross, Samoson, Massiot, JACS 124 5634-5635 (2002)

Excitation of Quadrupolar Nucleides

pulse duration (µs)

Intensité (a.u.)

-1.00 -0.50 0.00 0.50 1.00

0.00 5.00 10.00 15.00 20.00

250 0 -250

(kHz)

27

_{Al in}

α

_-Al

2

O

3

nutation spectrum

ν

1

=121 kHz, Offset=0, C

Q

=2.38 MHz

Adapted from Kentgens et al.

Solid State NMR

,

3

315 (1994)

Quantitative acquistion of CT

Central

Transition

I=3/2

(null offset)

pulse duration (µs)

Intensité (a.u.)

-1.00 -0.50 0.00 0.50 1.00

0.00 5.00 10.00 15.00 20.00

To extract quantitative data from the simulation of multisited

systems the excitation regime must be known.

 

A linear regime of excitation (independent of

ν

_Q

) is only

possible for small pulse angles (Freude, Man…).

α

<

π

/2(2I+1)

α

<

π

/8 for I=3/2

Nutation

Central

Transition

I=3/2

(null offset)

pulse duration (µs)

Intensité (a.u.)

-1.00 -0.50 0.00 0.50 1.00

0.00 5.00 10.00 15.00 20.00

ν

Q

>>

ν

1

(I+1/2)

ν

1

.

ν

Q

<<

ν

1

ν

1

ν

Q

~

ν

1

ν

Q

<<

ν

1

non selective regime (liquid like) sine behavior of the whole system of transitions.

Solid Quadrupolar Echo

π

/2

(x)

-

τ

-

π

/2

(y)

- acqu

ν

Q

~

ν

1

intermediate regime, non pure sine behavior, excitation of multiple quanta.

multiquanta excitation

θ

1 -

τ

-

θ

2 - acqu

ν

Q

>>

ν

1

selective regime, the central transition can be approximated as an isolated fictitious

spin 1/2 with a nutation frequency of (I+1/2)

ν

1

.

Hahn-Echo -

π

/2 -

τ

-

π

- acqu

Central Transition - Hahn (whole) Echo

1

-1

π/2

π

τ

_τ

Echo

Acquisition

t

₂

I=3/2

Hahn Echo – Full Echo - Central Transition

Magnitude

Full Echo FT

Real

Imaginary

71

_{Ga (I=3/2) in}

β

_-Ga

2

O

3

τ

=200µ

 

Signal is acquired from -

∞

to +

∞

(beginning null, ending null).

 

Gain of up to 2

1/2

_{in signal to noise (negative and positive time of the echo).}

 

Time shift is retrieved from first order phase (shift in time).

 

Imaginary part (odd) is null. Phasing can be carried out automatically or by adjusting the

imaginary part to null (phase 0 and phase 1).

 

Magnitude spectrum is not distorted

Usefull for very wide spectra when the loss in intensity (due to

τ

)

is minimum with

short lasting FIDs

MAS is not always giving resolution

D.Massiot, I.Farnan, N.Gautier, D.Trumeau, A.Trokiner, J.P.Coutures

"

A 71Ga and 69Ga study of b -Ga2O3 : resolution of four fold and six fold coordinated Ga sites in static conditions.

"

Solid State NMR

4 241-248

1995

-1500 -1000 -500 0

500 1000 1500

2000 (ppm)

71

_{Ga - 7 T}

_*

*

*

*

*

*

*

*

71

_{Ga - 11.7 T}

Ga

_IV

model

Static

MAS 15 kHz

-3000 -2000 -1000 0 1000 2000 3000

ppm

Ga VI

Central Transition - Hahn (whole) Echo

1

-1

π/2

π

τ

_τ

Echo

Acquisition

t

2

I=3/2

ν

1

selective=2

ν

1

Δθ1 Δθ9

+k Δθ10 +k Δθ6 Δθ2 0 0.0 0.2 0.4 0.6 0.8 1.0 0.6

0.2 0.4 0.8 1.0

Pitch

Θ/2π

θq/2π

1

-1

Δθ1

Δθ3

Δθ8

Magic Angle Spinning -

2nd

_order

(

)

_∑

(

)

=

φ

+

ω

−

β

α

>

−

<

=

ν

+

θ

−

ν

+

ν

2

1

n

t

n

i

n

,

Q

2

0

1

m

,

m

C

A

e

r

2

)

m

2

1

(

Cos

P

First order

H

I

<<

H

z

P

4

(cos

θ

)

(

)

_∑

(

)

∑

₌

−

ω

+

φ

=

>

−

<

=

ν

+

θ

+

ν

4

1

n

t

n

i

)

2

(

n

4

,

2

,

0

l

l

)

2

(

l

l

I

,

m

0

1

m

,

m

C

B

P

Cos

A

e

r

Second order

H

I

<

H

z

MAS

54.74°

P

2

(cos

θ

)

2D Isotropic experiments for Quadrupolar nuclei

φ

R

π/2

φ

1

β

1

β

₂

t

₁

π/2

φ

2

π/2

φ

3

t

₂

Angle

switch

30 ms

P

4

(cos

θ

)

P

₂

(cos

θ

)

θ

0°

static

1

-0.5

90°

DAS

DAS

DAS

17

_{O DAS in SiO}

2

crystalline Coesite

P.Grandinetti & al.

J. Phys Chem Soc

1995

φ

R

π/2

φ

1

β

1

β

2

t

1

π/2

φ

2

π/2

φ

3

t

₂

Angle

MQ-MAS – L. Frydman 1995

L. Frydman & al.

ENC 1995, Boston, J. Am. Chem Soc

1995,

117

, 5367

DAS, MQ-MAS & STMAS

0

-3 +3

3Q 1Q t1 t2

0 -1 +1

t1 hop t2

θ1 θ2

Pulse sequence

Coherence pathway

DAS

MQ-MAS

angle

0 -1 +1

t1 t2

Sat Central

STMAS

Pulse duration (µs)

Intensity (a.u.)

-1.00 -0.50 0.00 0.50 1.00

0.00 5.00 10.00 15.00 20.00

1 kHz 25 kHz

50 kHz

100 kHz 250 kHz

1000 kHz

I=3/2

( ) (

)

Ω

p

l

p

l

l

l

C A

P

= −

=

∑

0 2 4

, ,

,

cos

isotropic/anisotropic DAS, MQ-MAS & STMAS

pulse sequence coherence pathway 0 -3

+3 3Q 1Q

t1 t2

MQ-MAS

(Frydman 95)

DAS

(Llor&Virlet, Pines 88)

0 -1 +1

t1 hop t2

θ1 θ2

angle

-1 +1 0

t1 t2

Sat Central

STMAS

(Gan 2000)

φ

R

π/2

φ

1

β

1

β

₂

t

1

π/2

φ

2

π/2

φ

3

t

2

Mirror Image evolution provides cancelation of 2

nd

_order

broadening, while maintaining isotropic resolution

P.J.Grandinetti

(

)

_∑

(

)

∑

=

φ

+

ω

−

=

>

−

<

=

ν

+

θ

+

ν

4

1

n

t

n

i

)

2

(

n

4

,

2

,

0

l

l

)

2

(

l

l

I

,

m

0

1

m

,

m

C

B

P

Cos

A

e

r

 

technically challenging

 

hop time is long (~30ms)

diluted spin systems

(Zwanziger

11

_B)

 

Valid for large couplings

CT as a fictituous spin ½

(Baltisberger, Grandinetti)

 

17

_O,

87

_Rb,

11

_{B (diluted),}

71

_Ga

 

easy to implement,

lots of different excitation

(nutation, RIACT, amp.

modulation, freq. sweep...)

 

suitable for abundant

nuclei (

27

_Al)

 

Intermediate couplings :

needs high rf powers ?

 

27

_Al,

23

_Na,

17

_O,

87

_Rb,

11

_B,

71

_Ga

 

accurate MAS angle

(1/100°) and spinning rate

 

suitable for abundant

nuclei (

27

_Al)

 

Intermediate to large

couplings

 

27

_Al,

23

_Na,

17

_O,

45

_Sc,

93

_Nb

Different spreading of the spectrum & scaling of δ

iso

CS/2

nd

Order Quad. shift

MQ-MAS RbNO

₃

(ppm) 0

-20 -40 -60 -80

Experimental Modèle

-75

-50

-25

0

(ppm)

MQ-MAS Baltisberger et al. (1992) Site _δCSISO

(ppm) CQ (MHz) ηQ δCS

ISO

(ppm) CQ (MHz) ηQ

#1 -31.3 1.79 0.55 -30.9 1.85 0.48

#2 -26.6 1.75 0.18 -26.2 1.83 0.12

#3 -28.5 1.99 0.91 -26.8 2.07 1.0

site #1

site #2

site #3

-75

-50

-25

0

(ppm)

Experimental

Modèle

#1

#2

#3

MAS

D.Massiot, B.Touzo, D.Trumeau, J.P.Coutures, J.Virlet, P.Florian, P.J.Grandinetti "Two-dimensiontal Magic-Angle Spinning Isotropic Reconstruction Sequences for Quadrupolar Nuclei."

Ultimate resolution at ultra high field (40T)

80

40

0

-40

MQ-MAS 400

(ppm)

STMAS 830

(ppm)

40

20

0

-20

-40

27

_{Al A}

9

B

2

Models

experimental

Gan, Gor’kov, Cross, Samoson, Massiot, JACS

124

5634-5635 (2002)

NHMFL – Z. Gan

Hours / Minutes

J/D Couplings in Solid State NMR

Q

₂

Q

₁

Dipolar

through space

distances

~kHz 1/r

3

Q

2

Q

1

J Coupling

through bond

chemical bonding

<100s of Hz

Isotropic Part of Interaction

 

small but remain when spinning fast @

MAS

 

need long T’

₂

to develop

 

Pulse sequence (liquid like) are simple and

involve few rf powers

 

Usually ignored in most inorganic solids

Anisotropic Interaction

 

larger but need to be reintroduced

 

suffer limitation with spinning rate or spin

lock possibilities – T

_1ρ

for quadrupoles

 

Pulse sequence may be complex and often

involve large rf powers

 

Hard to transpose to quadrupoles

Recoupling ?

19F homonuclear correlation

-170 -160 -150 -140 -130 -120 -110 -170

-160

-150

-140

-130

-120

-110

F8 F4 F3 F9 9 F6 F2 2 F7 7 _F10 F5 F1

F10-F8

3.587 Å

F6-F8 3.491 Å F4-F2

2.501 Å

F6-F1 2.473 Å 3.120 Å

M. Deschamps, F. Fayon, S. Cadars, A. L. Rollet, D. Massiot, PCCP2011, 13, 8024.

DH

3

_{(No recoupling)}

B

0

= 17.6 T (750 MHz)

ν

_ROT

= 66.7 kHz

19

_{F CS range ~ 60 ppm}

19

_{F CSA ~ 80-110 ppm}

19

_{F in BaAlF}

5

40.5 kHz

Probing distances up to 3.6 Å

(dipolar truncation)

Short DQ excitation times

(2τ = 197 µs)

SnP

₂

O

₇

31

_P/

31

_{P Dipolar or J correlation}

F.Fayon, I.J.King, R.K.Harris, R.B.K.Gover, J.S.O.Evans, D.Massiot

"Characterization of the room temperature structure of SnP2O7 by 31P through-space and through-bond NMR correlations spectroscopy." Chem. Mater. 15 2234-2239 2003

-28 -32 -36 -40 -44

-60 -64 -68 -72 -76 -80 -84

Simplification of the J-mediated correlation

108 different P sites (54 pairs)

P2

₁

or

Pc

space groups

Dipolar DQ/SQ spectrum

Refocused J-INADEQUATE

-28 -32 -36 -40 -44

-28 -32 -36 -40 -44

MP

₂

O

₇

family : model of negative thermal expansion materials

SnP

2

O

7

AlPO

₄

J-Resolved - Figure 1

t

₁

/2

t

₁

/2

t

₂

27

_Al

31

_P

-200 0

200 0

(Hz)

T

*

2

=14.4ms

J=21.8 Hz

T

2

=13.2 ms

(c1)

(c2)

(c3)

(b1)

0 0.2 0.4 0.6 0.8 1

10 20 30 40 50 (ms)

(a)

(b2)

D.Massiot, F.Fayon, B.Alonso, J.Trebosc, J.P.Amoureux

Chemical bonding differences evidenced from J coupling in solid state NMR experiments involving quadrupolar nuclei.

t

₁

/2

t

₁

/2

t

₂

27

_Al

31

_P

J=21.8 Hz

T*

2

=14

±

1 ms

0 0.2 0.4 0.6 0.8 1

10 20 30 40 50 (ms)

(a)

-100 -50

0 50 100

(Hz)

(c2)

(c4)

(c1)

(c3)

J

1

=26.5

±

1 Hz

J

2

=18.5

±

1 Hz

T

2

=14

±

1

ms

(b1) J=21.8 Hz

T*

2

=14

±

1 ms

(b2) J

1

=26.5

±

1 Hz

J

2

=18.5

±

1 Hz

T

2

=14

±

1

ms

D.Massiot, F.Fayon, B.Alonso, J.Trebosc, J.P.Amoureux

Chemical bonding differences evidenced from J coupling in solid state NMR experiments involving quadrupolar nuclei.

J. Magn. Reson.164 165-170 (2003)

AlPO

₄

HMQC – figure 2

27

_Al

31

_P

t

₁

/2

t

₁

/2

t

₂

τ

τ

27

_Al

31

_P

27

_Al

31

_P

(ppm) 56 40 24 8

(ppm)

-20 -24 -28 (ppm)

-20 -24 -28

(a)

(b1)

Exp.

(b2)

Model

-25

0

25

50

75

25

(ppm)

(c1)

(c2)

(c3)

J-Coupling - Spin Counting

27

_Al/

31

_P

n

27

_Al

31

_P

t

2

τ

τ

27

_Al

DFS

31

_P

31

_P

₂₇

Al

D.N.Shykind, J.Baum, S.B.Liu, A.Pines JMR 76 149-154 1988 – K Saalwachter et al. 2007

M.Deschamps, F.Fayon, J.Hiet, G.Ferru, M.Derieppe, N.Pellerin, D.Massiot

"Spin-counting NMR experiments for the spectral editing of structural motifs in solids"

Phys. Chem. Chem. Phys. 10 1298-1303 2008

Δφ

Spin Counting in the Al(OPO

₃

)

₄

motif

IS

₄

“liquid” like spin system

J

₁

=

J

₂

= 25.9 Hz &

J

₃

= J

₄

= 23.4 Hz

(including the residual dipolar contribution due to the offset in the spinning angle)

AlPO

4

Berlinite

normalized

Counting from J & dipolar – MAS & Static

Scalar Coupling

Dipolar

Static

35ms

16ms

2ms

T

₂

’

(measured as the decay

of the sum of each

nQ pathway)

100%

29

Si Anorthite

Glass

M.Deschamps, F.Fayon, J.Hiet, G.Ferru, M.Derieppe, N.Pellerin, D.Massiot,

Physical Chemistry Chemical Physics

10

1298-1303

2008

From one to three tetrahedra

F. Fayon, I.J. King, R.K. Harris, J.S.O. Evans, D. Massiot

Comptes Rendus de Chimie

7

351-361 (2004)

F.Fayon, C.Roiland, L.Emsley, D.Massiot,

Journal of Magnetic Resonance

179

50-58 (2006)

t

1

t

1

t

2

JRES

Q

1

Q

₂ 0 -8 -16 -24 -32

40 0 -40

J

₂

~

17

to

25

Hz

750 Hz 1200 Hz

~ 2Å

-40 -30 -20 -10 0

Q

1

_-Q

1

Q

1

_-Q

2

Q

2

_-Q

2

INADEQUATE

~ 5Å

τ

τ

τ

t

1

τ

t

2

3Q INADEQUATE

(ppm)

-40 -30 ) -20 -10 0

Q

2

_-Q

2

_-Q

2

Q

1

_-Q

2

_-Q

2

Q

1

_-Q

2

_-Q

1

~ 7-8Å

τ

τ

τ

t

1

τ

t

2

(PbO)

0.61

(P

2

O

5

)

0.39

Molecular Units in Solids

a b

c

Increasing size of molecular units

Matériaux à différentes échelles

Å

nm

Homogène / Isotrope

Hétérogène / Anisotrope

2

nm

3 - 4

nm

O H-O

Matériaux à différentes échelles

Å

nm

Homogène / Isotrope

Hétérogène / Anisotrope

2

nm

3 - 4

nm

O H-O

Si Si O O _O

Homogène / Isotrope

H

H

H

H

Hétérogène / Anisotrope

 

Homogénéité

 

Nucléation / Croissance

 

Viscosité

 

Configuration

 

Chimie

 

Transition Vitreuse

 

Modélisation

3 - 4 nm

 

Surface

 

Interface

 

Porosité

 

Liaisons H

 

Greffage

 

Réactivité

 

Fonctionnalisation

 

Vectorisation

TGIR RMN THC