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EPSRC UK National Solid-state NMR Service at Durham
Solid-state NMR: Basic Principles, Practice, Interpretation and Applications 2015
Interpretation and Applications
EPSRC UK National Solid-state NMR Service at Durham
The spectrum
However, the general appearance of a spectrum can give us lots of basic information about the sample.
The properties of solid-state spectra are more sample-dependent than solution-state ones.
Questions on what is possible to say about a sample using solid-state NMR can usually only be answered with confidence once a spectrum has been obtained.
EPSRC UK National Solid-state NMR Service at Durham
12
CP
EPSRC UK National Solid-state NMR Service at Durham
The spectrum
EPSRC UK National Solid-state NMR Service at Durham
The spectrum – spinning sidebands
Spinning sidebands
“Rigid” solid
EPSRC UK National Solid-state NMR Service at Durham
The spectrum – spinning sidebands
Identifying sidebands
Look for repeating patterns …
… separated by the spin rate
nr
nr
Confirm by changing the spin rate
EPSRC UK National Solid-state NMR Service at Durham
The spectrum – line widthNarrow lines
Crystalline (if rigid)
Possibly soft (poor CP, no/weak sidebands)
EPSRC UK National Solid-state NMR Service at Durham
The spectrum - purity
No small signals
Probably pure(in SSNMR terms)
EPSRC UK National Solid-state NMR Service at Durham
The spectrum
One molecule per crystallographic asymmetric unit
23 carbon sites
19 clear resonances
EPSRC UK National Solid-state NMR Service at Durham
The spectrum - identification
How can we tell if this is the “right” spectrum?
EPSRC UK National Solid-state NMR Service at Durham
The spectrum – solid- vs. solution-state
EPSRC UK National Solid-state NMR Service at Durham
The spectrum – assignment
Correlation chart
ppm from tetramethylsilane
EPSRC UK National Solid-state NMR Service at Durham
The spectrum – assignment
ppm from tetramethylsilane
~
EPSRC UK National Solid-state NMR Service at Durham
The spectrum – assignment
EPSRC UK National Solid-state NMR Service at Durham
The spectrum – assignment
EPSRC UK National Solid-state NMR Service at Durham
The spectrum – assignment
EPSRC UK National Solid-state NMR Service at Durham
The spectrum – assignment tools
Interrupted decoupling
EPSRC UK National Solid-state NMR Service at Durham
The spectrum - polymorphism
Observed spectrum
Known shifts for polymorph III
Omitted
EPSRC UK National Solid-state NMR Service at Durham
The spectrum - polymorphism
Known shifts for polymorph I
EPSRC UK National Solid-state NMR Service at Durham
EPSRC UK National Solid-state NMR Service at Durham
Multi-component systems
Inevitably, the question of quantification will arise!
EPSRC UK National Solid-state NMR Service at Durham
Multi-component systems – quantification of a mixture
Spectra should be recorded so that both components are at full intensity (fully relaxed). RD = 5×T1
H(longest)
EPSRC UK National Solid-state NMR Service at Durham
Multi-component systems – quantification of a mixture
Identify one (or more) pairs of resonances to represent the components
EPSRC UK National Solid-state NMR Service at Durham
Intensity vs. contact time
HXH( ) exp( / ) exp( / )S t S t T t T r
é ù= - - -ë û0 11
EPSRC UK National Solid-state NMR Service at Durham
T1r
“Spin-lattice relaxation in the rotating frame”
Where T1 is the relaxation in the intense static field, T1r is the relaxation in the magnetic field associated with an RF pulse
T1 T1r
Frequency of motion causing relaxation MHz kHz
Timescale of relaxation seconds milliseconds
EPSRC UK National Solid-state NMR Service at Durham
Intensity vs. contact time
HXH( ) exp( / ) exp( / )S t S t T t T r
é ù= - - -ë û0 11
Different components may have different properties so we need to model the behaviour of the intensity as a function of contact to extract S0.
S0 = S (t = 0) is the intensity in the absence of relaxation – and is the value we need to compare intensities from different components.
EPSRC UK National Solid-state NMR Service at Durham
Intensity vs. contact time
Extrapolate the long-contact behaviour
Equal intensity
EPSRC UK National Solid-state NMR Service at Durham
Multi-component systems - quantification
The alternative is to ignore differences between the components and plot a calibration graph based on samples with known composition.
unkn
own
Another inevitability: what are the errors?
EPSRC UK National Solid-state NMR Service at Durham
Multi-component systems - quantification
Only by replicating measurements can you have real confidence in the errors.
unkn
own
EPSRC UK National Solid-state NMR Service at Durham
Amorphous materials
Crystalline
Amorphous
Dn½ = 28 Hz
Dn½ = 223 Hz
EPSRC UK National Solid-state NMR Service at Durham
Amorphous materials
polyethylene
polysaccharide
EPSRC UK National Solid-state NMR Service at Durham
Semicrystalline polymers
2.2 T1rho filterDP 1s
15us T2 filter
T1r(H) filter 2.2 ms Rigid, o
rder
ed
EPSRC UK National Solid-state NMR Service at Durham
Intensity vs. contact time
Delayed contact
EPSRC UK National Solid-state NMR Service at Durham
Semicrystalline polymers
2.2 T1rho filterDP 1s
15us T2 filter
T1r(H) filter 2.2 ms
DE 1s
T2(H) filter 15 ms
Rigid, o
rder
ed
Soft
Rigid, d
isord
ered
EPSRC UK National Solid-state NMR Service at Durham
Dynamic systems
EPSRC UK National Solid-state NMR Service at Durham
Dynamic systems
EPSRC UK National Solid-state NMR Service at Durham
Dynamic systems
4
3
1
2
Broad – motion?
To be consistent with the NMR data, the proton must jump from N1 to N2. This is accompanied by a rotation of the tetrazole ring – interchanging N3 and N4 (and making the start and finish arrangement indistinguishable by X-ray)
EPSRC UK National Solid-state NMR Service at Durham
Elements with spin
EPSRC UK National Solid-state NMR Service at Durham
“Easy” elements
EPSRC UK National Solid-state NMR Service at Durham
EPSRC UK National Solid-state NMR Service at Durham
Intensities from overlapping lines - deconvolution
EPSRC UK National Solid-state NMR Service at Durham
Silicon-29
Direct excitation
Quantitative
EPSRC UK National Solid-state NMR Service at Durham
Silicon-29
m,m ,m
m m/I I
= =å å=4 4
4 440 0Si / Al
EPSRC UK National Solid-state NMR Service at Durham
Deconvolution
EPSRC UK National Solid-state NMR Service at Durham
Deconvolution
( )observed simulatednx xc å= -
22
Line widths : 220 - 250 Hzχ2 = 129,000
-97.4 -102.4 -107.8
22% 54% 24%
EPSRC UK National Solid-state NMR Service at Durham
Deconvolution
-90.3 -93.6 -97.4 -102.4 -107.8 -111.5 -99.1
22% 54% 24%
3% 3% 23% 47% 22% 2%
Line widths : 220 - 370 Hzχ2 = 129,000χ2 = 26,000
EPSRC UK National Solid-state NMR Service at Durham
Deconvolution
Line widths: 150 - 320 Hz, 850 Hzχ2 = 129,000χ2 = 26,000χ2 = 14,000
-90.3 -93.6 -97.4 -102.4 -107.8 -111.5 -99.1
22% 54% 24%
3% 3% 23% 47% 22% 2%
5% 34% 18% 2% (41%)
EPSRC UK National Solid-state NMR Service at Durham
Silicon chemical shifts
SiR
O
R
O Si
O
R
R
SiXO
O
R
OX Si
OXR
OO
SiXO
O
R
O Si
O
R
O Si
R
OO
SiO
O
O
O
SiO
O
O
OH
SiO
O
OH
OH
EPSRC UK National Solid-state NMR Service at Durham
Boron (11B spin-3/2)
EPSRC UK National Solid-state NMR Service at Durham
Boron (11B spin-3/2)
EPSRC UK National Solid-state NMR Service at Durham
Boron (11B spin-3/2)
Bandshape fit:Cq = 1.45 MHzη = 0iso = -23.5 ppm
EPSRC UK National Solid-state NMR Service at Durham
Aluminium (27Al, 100%, spin-5/2)
Framework
Extra-framework
EPSRC UK National Solid-state NMR Service at Durham
Aluminium (27Al, 100%, spin-5/2)
5?
EPSRC UK National Solid-state NMR Service at Durham
Aluminium (27Al, 100%, spin-5/2)
MQMAS
M = 3
EPSRC UK National Solid-state NMR Service at Durham
Heavy metals
EPSRC UK National Solid-state NMR Service at Durham
Coupling
Residual dipolar coupling (between 13C and 14N)
EPSRC UK National Solid-state NMR Service at Durham
Coupling
Dipolar coupling – through space – distance measurement
“Recouple” – rotor synchronised elements of a pulse sequencee.g. REDOR
EPSRC UK National Solid-state NMR Service at Durham
1H
Natural “resolution”
H-bond
EPSRC UK National Solid-state NMR Service at Durham
1H
Natural “resolution”
H-bond
EPSRC UK National Solid-state NMR Service at Durham
1H
60 kHz
EPSRC UK National Solid-state NMR Service at Durham
1H
60 kHzHRMAS
EPSRC UK National Solid-state NMR Service at Durham
Solid-state NMR in the UK
EPSRC UK National Solid-state NMR Service at Durham.
The UK 850 MHz Solid-state Facility at Warwick.
For the NMR expertYou provide the sample we take care of the NMR
EPSRC UK National Solid-state NMR Service at Durham
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