Matériaux hybrides : nouvelles perspectives d’études
par RMN à très hauts champs
molecular recognition
H-bonding
(EtO)3Si
hydrolysis
O 1.5 Si
Si(OEt)3
condensation
SiO 1 .5
n
hybrid material
C. Bonhomme, C. Gervais, C. Coelho, T. Azaïs, N. Baccile, G. Laurent,
L. Bonhomme-Coury and F. Babonneau
Université P. et M. Curie, France
Laboratoire de Chimie de la Matière Condensée de Paris
UMR CNRS 7574
TGIR-RMN : réunion des utilisateurs – Paris, 1er octobre 2009
Hybrid materials: a combined NMR / ab initio calculations approach
advanced solid state
NMR techniques
Bo
keywords:
* multinuclear NMR
* multidimensional
* MACS
first principles
calculations
structural models
keywords:
keywords:
* CSA tensors
* computer modelling
* Q tensors
* VASP
* J tensors
* orientations
materials
* amorphous materials
* substitutions
♦ DIPOLAR INTERACTION D
rIS
D ∝
molecular recognition
H-bonding
(EtO)3Si
1
rIS3
750!
Bo
hydrolysis
O 1.5 Si
CEMHTI,
Orléans
Si(OEt)3
condensation
SiO 1 .5
n
33 kHz
67 kHz
hybrid material
■ 1H-1H dipolar interaction
Chem. Soc. Rev., 38 (2009) 1608
■ ureidopyrimidinone models
■ bio-inspired materials
Ureidopyrimidinone based systems
biomolecular
assembly
XRD of precursors
hydrolysis
O
Me
ureidopyrimidinone
derivatives
N
N
H
O
Si(OEt)3
N
H
N R
H
inorganic
pillars
H-bonding
Collaboration: B. Alonso, D. Massiot,
M. Wong Chi Man / Orléans - Montpellier
Ureidopyrimidinones: 1H high resolution solid state NMR
Bo
O
Me
400
N
15 KHz
N
H
N H
O
N
H
R
(EtO)3Si
?
C R-Si(OEt)3
D
H
O
H
N
750!
A, B, C, D
O
Me
N
N
A H
N
H
B B
N
H
N
H
N
H
O
Me
O
N
(EtO)3Si
33 KHz !
R
C
H
ppm
20
10
0
G. Arrachart, B. Alonso, D. Massiot,
C. Bonhomme et al., Chem. Eur.
Journal 15 (2009) 5002
-10
Application to ureidopyrimidinone precursors
excitation
reconversion
t1
1H
synchronization
with MAS
τR/2 τR/2
n
BAck to BAck
t2
τR/2 τR/2
n
2Q hamiltonian !
Application to ureidopyrimidinone derived materials: hybrid silica
Towards bio-inspired materials: adenine (A) and thymine (T) derivatives
1H
BABA NMR
750 MHz/33 KHz
G. Arrachart, B. Alonso, D. Massiot, C. Bonhomme et
al. J. Mater. Chem. 18 (2008) 392
♦ low gamma nuclei
♦ low mass samples
Collaboration: S. Laurencin, D. Laurencin,
F. Fayon, D. Massiot / Montpellier Orléans
Dipolar MAS experiments:
43Ca
–
13C
proximities
> 5.6 Å
C11
C7
1H
4.8 Å
C17
C7
C7 C17
C17
S0
S
2.9 Å
13C
C11
C11
43Ca
174.9
ppm
C
13
173.2
ppm
0.8
strong TRAPDOR
dephasing!
C7 Short range
43
Ca…13C
distances
0.7
0.6
(S0-S)/S0
OFF
0.5
C17
0.4
0.3
Longer range
43
Ca…13C
distances
0.2
ON
0.1
190
180
(ppm)
170
160
150
D. Laurencin, D. Massiot, C. Bonhomme
et al. J. Am. Chem. Soc. (2009)
0
0
10
20
30
40
2τ (ms)
50
60
70
Natural hydroxyapatite samples: mouse teeth
φ 1.3mm ultra fast MAS probe: 1H,
31P, 23Na
...
‐10
‐8
‐6
‐4
‐2
31P-1H
hetcor, CT=1ms
50 kHz MAS
Expt=3h!
0
2
OH
mouse tooth
1H (ppm)
4
H2O
6
8
10
12
14
16
750!
18
20
22
CEMHTI,
Orléans
24
20
16
12
8
4
31P
0
(ppm)
‐4
‐8
‐12
D. Laurencin, S. Laurencin, F. Fayon, C. Coelho
‐16
δ33 Z
T
δ22
δ11
P,29Si
δiso
ΔCSA
ηCSA
31
YT
Exp.
Calc.
XT
ppm -100
-150
-200
-250
Si
P
Si
Pickard, Mauri, Phys. Rev. B (2001).
GIPAW
First principles calculations: the GIPAW approach
Pickard, Mauri, Phys. Rev. B (2001)
GIPAW
T. Charpentier et al.
R. Dupree et al.
DFT
periodic systems
R. K. Harris et al.
evaluation of j(1)(r’) using pseudopotentials
Bin
= 1/c ∫
d3r’
j(1)(r’)
inorganic and organic
I. Farnan et al.
all-electron hamiltonians
(1)(r)
M. Profeta, C. J. Pickard, F. Mauri et al.
r-r’
×
|r-r’|3
CSA
derivatives...
S. Ashbrook et al.
J. W. Zwanziger et al.
F. Boucher et al.
...
1H
molecular recognition
H-bonding
EFG
! J !
IDRIS
hydrolysis
δ,
CSA,
Si(OEt)3
(EtO)3Si
condensation
tensors
O 1.5 Si
SiO 1 .5
n
Gervais et al., Phys. Chem. Chem.
Phys. 11 (2009) 6953.
J,
hybrid material
Bonhomme, Gervais et al., Chemical Reviews: accepted proposal (march 2009)
...
More from 1H GIPAW data: H-bonding and CSA tensors
1H
isotropic chemical shifts
Brushite: CaHPO4.2H2O
H3
H2
H2
δ22
δ33
H3
Ca
δ33
δ22
H5
δ22
δ33
H4
δ33
δ22
δ22
HH1
1
P
Ca
δ
δ3333
O-H...O direction
Ca
P
H-bonding in calcium phosphates
and phosphonic acids
Gervais et al., J. Magn. Reson. 187 (2007) 181.
1H
CSA tensors and orientations
Pourpoint et al., Appl. Magn. Reson. 32 (2007) 435.
Hydroxylated silica surface: towards interfaces
amorphous slab
δ(29Si) (ppm)
(∼ 13Å × 18Å × 10Å)
-80
Si
CQ(17O) (MHz)
H
GIPAW calculations
-90
-100
29Si
-110
NMR
-120
-130
O
Q4
Q3
Q2
-70
7.5
7
6.5
6
5.5
5
4.5
4
110
130
135
140
145
150
Si-O-Si angle (°)
155
17O
120
130
140
150
160
170
180
NMR
Si-O-Si angle (°)
Clark et al., Solid State NMR 16 (2000) 55.
∼ 6 OH/nm2
∼ 30% of geminal silanols
∼ 40% involved in H-bonds
F. Tielens, C. Gervais et al., Chem.
Mater. 20 (2008) 3336.
δ(1H) SiOH (ppm)
CQ = a (0.5 + cosα/(cosα-1))b + m(d-d0)
5
4
3
1H
2
NMR
1
0
1.6
1.8
2
2.2
2.4
2.6
2.8
3
OH ... O (Å)
„ adsorption of organic molecules on silica
„ other surfaces: amorphous CaP « ACP »
29Si, 31P
P →
31
and
17O
CSA and Q parameters: Si5O(PO4)6 and SiP2O7
N.A.
Si static CP
29
P
SiO2
Si
Calc.
* : ZrO2
-140
Bo
-160
-180
(ppm)
*H3PO4
-200
-220
*
*
Exp.
-240
Si
Calc.
O
-120
MAS experiment
Si5O(PO4)6
Exp.
-100
17O
O5
O4
δiso
O3
ΔCSA
ηCSA
O2
200
150
100
50
0
-50
Exp.
Calc.
Collab. L. Montagne, G. Tricot,
31P
-44.0 ppm
P-17O-Si
L. Delevoye, Lille, France
800 MHz spectrometer
O1
ppm
Si-17O-Si
Ultra fast MAS experiments and J couplings (exp. / GIPAW)
β-Ca(PO3)2
γ-Ca(PO3)2
F. Pourpoint
Collaboration: F. Fayon, J. Yates /
Orléans - Cambridge
good agreement between the exp. and
calculated isotropic J values (to see:
ΔJ, PAS...)
31P