Physical Methods in Inorganic Chemistry Magnetic Resonance: Lecture Course Outline Lecture 1: A Quick Reminder

Physical Methods in Inorganic Chemistry
Magnetic Resonance
Physical Methods Magnetic Resonance
Lecture Course Outline

Lecture 1:
A quick reminder
A few trends in Inorganic NMR
A little more on Chemical Exchange
Essential NMR Methods
Spin Decoupling
Spin Relaxation Measurements (again and more)
Lecture 2:
NMR Methods continued 2D and others

Correlated Spectroscopy (COSY)
Nuclear Overhauser (NOE)
Magic Angle Spinning (MAS)
Lecture 3:
Electron Paramagnetic Resonance

The why and when of EPR in Inorganic Chemistry
EPR methods (ENDOR, DEER)
Physical Methods in Inorganic

Chemistry
Magnetic Resonance
Literature
H. Friebolin
H. Gnther
P. J. Hore
A. K. Brisdon
C. P. Slichter
R. Freeman
One and Two Dimensional NMR Spectroscopy

NMR Spectroscopy
Nuclear Magnetic Resonance (primer)
Inorganic Spectroscopic Methods (primer)
Principles of Magnetic Resonance
Spin Choreography
Website and e-mail:

http://timmel.chem.ox.ac.uk
timmel@physchem.ox.ac.uk
Magnetic
Resonance
Selected NMR properties of some

elements
Gyromagnetic ratio
(107 rad T-1s-1)
26.75
8.58
6.72
1.93
-2.71
29.18
6.98
-5.31
10.84
7.05
6.35
5.12
-0.85
-1.25
-10.02
6.43
-8.50
1.12
0.50
5.80
4.82
Trends in Chemical Shifts

Remember: The diamagnetic shielding generally
becomes smaller as the electron density at the nucleus
decreases.
Thus electronegative substituents, positive charge or
increase in oxidation state usually result in decreased
shielding and increased shift.
Opposite effects may be observed for transition metals (ligand effects).
Effect of Charge, Substituents

and Oxidation State
The effect of coordination on the

chemical shift of a transition metal
Remember
1. The paramagnetic shielding contribution p ~ 1/E
2. paramagnetic currents AUGMENT the magnetic field (p is
negative, hence a DESHIELDING parameter!)
/ ppm
E / cm-1
Co(PF3)3-
-4200
Co(CN)63-
26300
Co(NH3)63+
6940
23210
Co(en)33+
7010
21400
Co(NO2)63-
7350
20670
Co(acac)3
12300
16900
p|*
Typically, shifts follow the spectrochemical series: strong field

ligands give small or negative chemical shifts whilst halogens
give larger chemical shifts.
Chemical Exchange
Remember:
( A B )
k
2
Examples of Fluxional inorganic systems.
Axial-equatorial exchange in trigonal bipyramidal systems
(PF5, SF4, PF4NMe2 , Fe(CO)5)
Bridging/axial exchange in carbonyls.
Bridging terminal exchange in boranes (B2H6 etc.);borohydrides (Al(BH4)3)
Ring-whizzing in 1-cyclopentadienides (Cu(PMe3)( 1-C5H5)
Interchange of ring bonding modes in compounds with mixed heptacity
( e.g. (1-C5H5)2(5C5H5)2Ti: (4-C6H6)(6-C5H5)Os
17
O spectrum of Co4(CO)12
The 31P spectrum of PF4N(Me)2
All 19F equivalent at high Temperature
Fa
Fe P
Fa
N(Me)2
Fe
I(31P) = (19F) = 1/2
19
Fe and 19Fea not equivalent at low Temperature
C{H} spectrum of [(CH3)3C 6Li]4
13
Recall: multiplets
2nI + 1
I(6Li) = 1
Jav = (5.4 Hz 3 + 0)/4
= 4.1 Hz
x
J(13C-6Li) = 5.4 Hz
n=4
n=3
NMR Acronyms
Nuclear
Overhauser
Spectroscopy
Correlated
Spectroscopy
Electron Nuclear
Double
Resonance
Magic Angle
Spinning
Methods
Continuous wave
E
h
B
Spin Lattice Relaxation and The

Inversion-Recovery Experiment
Inversion Recovery Method
z
y
y
x
z
y
y
x
NMR Signal
I()
M z ( ) M 0 ( 1 2e
T1
Spin Spin Relaxation and the

Spin Echo Experiment
echo
y
x
x
y
y
x
s
m
f x
What is the effect of relaxation on

the echo amplitude?
Spin spin
Relaxation
random magnetic fields destroy phase

coherence and are not refocused by pulse
NMR Echo of each signal:

I ( 2 ) I ( 0 )e
2
T2
Echo Trains
The Method of Spin Decoupling
FACT: SpinSpin Coupling yields important information but

NMR data interpretation complicated by line splittings.
A SOLUTION: simplify spectra by removing some (chosen)
splittings and learn about which nuclei couple to which.
HOW: apply a second Radiofrequency source (S2) with
strength B2 in addition to transmitter S1 used for detection of
spectrum (a so-called double resonance experiment). S2 is
positioned at the resonance of a particular nucleus.
RESULT: decoupled spectra are less crowded and have
much higher sensitivity as all available NMR intensity
concentrated into single line (and Nuclear Overhauser).
The Origin of the Spin Decoupling Effect
I(X) = I(A) = 1/2
A
A
X( )
irrad at X
X( )
A( )
A( )
Notation: A{X}
A
Irradiation of X at its
resonance frequency
induces rapid transitions
from X( ) to X( ) and vice
versa. A sees a single,
averaged field.
B2 of same order as 2JAX
X should be sufficiently far
away from A
The Method of Spin Decoupling

i) irrad
ii) irrad
Fa
Fe A
Fa
Fluorine Spectrum I(19F) = 1/2

i) irrad
X
X
i) irrad
I(A) = I(X) = 0
ii) irrad
i)
Fe{Fa}
ii)
Fa{Fe}
31
31
P(CH3CH2O)3
irrad
P(CH3CH2O)3
31
I( P)=1/2
31
P(CH3CH2O)3
irrad
31
P(CH3CH2O)3
Recall: Exercise
B = 1.41T
Electron:
H:
N lower
N upper
g B B
1
0.904
kT
N lower
B
1
0.999855
N upper
kT
Can we
transfer this
polarisation?
The Nuclear Overhauser Effect

1) Enhancement of Sensitivity
ie, the heteronuclear (13C H) Nuclear Overhauser Effect
(1H) 26.75 107radT-1 s-1

(13C) = 6.72 107 rad T-1 s-1
2) Information about proximity of two nuclei (ie, protons)
3) Dependent on Cross Relaxation between different
spins. Prerequisite for this cross relaxation experiment is
that the spin lattice relaxation of the nuclei is dominated
by dipole-dipole interaction with the other nuclear spins.
The origin of the Nuclear

Overhauser Effect
Result: saturated proton transitions,

13
C population difference increased 3
fold
1
Irradiate proton resonances

2
ysical Methods Magnetic Resonance
0
13
sat
3
4
2
sat
13
5
Boltzmann
3
Protons saturated
4
Cross Relaxation
Takes spins from top to bottom
level, competition with 13C
relaxation (restoring Boltzmann
in 13C population)
The maximum attainable

enhancement (the fractional increase in
intensity)
maxI/S
where I is the saturated spin and S is the observed spin.
Maximum effect occurs when there is no leakage as a
result of relaxation mechanisms other than the dipoledipole interaction (a through space interaction!).
For homonuclear systems, maximum enhancement is 50%.
Remember that 15N and 29Si have negative .
Selective Nuclear Overhauser

enhancements
irrad
Difference Spectrum
Integration
29
SiH(Ph)3
Si107 rad T-1s-1

H107 rad T-1s-1
Si{1H}
29
Proton Decoupled
Coupled
Magnitude:maxI/S
~ -1.5
Principles of 2-Dimensional NMR
Father of 2D NMR: Jeener, Belgium

Main Developers: RR Ernst
(Switzerland),
R Freeman (UK, Oxford)
What we know from FT NMR
FT
2D NMR is a domain of FT and pulsed

spectroscopy
Principles of 2-Dimensional NMR

The time-intervals of 2D NMR
A 2-Dimensional Experiment
evolution
t1
evolution
t1
evolution
t1
Series of onedimensional
NMR spectra
must be
recorded
Amplitude Modulation
t1
t1
Phase Modulation
Fourier transformation of FID signal, S(t1, t2)

must be performed to obtain 2D spectrum
as function of two frequency variables S(F1, F2)
Larmor precession active during

t2, hence F2 contains chemical
shift
Spin-spin coupling was

active during t1, hence F1
contains coupling constant
What happens during the pulse

sequences?
x
t1
t2
Pulse Sequence
z
t1
x
y
y
x
What happens during the second x

Pulse?
/2x Pulse
Pulse does not affect x-component!
z
Pulse
Sequence:
t1
y
x
t2
y
x
t1
t2
=
y
x
A Simple 2D NMR Spectrum results

F2
F1
Correlated Spectroscopy (COSY)
Pulse Sequence
Aim : To discover spin-spin
couplings in a molecule.
Answer: Which resonance
belongs to which nucleus?
t1
t2
1
1
J ( A, X ) A2 : A J ( A, X )
2
2
1
1
X 1 : X J ( A, X ) X 2 : X J ( A , X )
2
2
A1 : A
Schematic COSY spectrum

of an AX system
Use of COSY to assign 11B NMR of B10H14.
(no couplings via H-bridges)

22
2
3=4
1=2
5=6=7=8
9=10
a
d
b
c
a: 2B coupled to all kinds of B

= 3,4
b: 4B coupled to 2 kinds of B
= 5,6,7,8
c: 2B coupled to 1 kind of B
= 9,10
d: 2B coupled to 2 kinds of B
= 1,2
2D-Nuclear Overhauser Spectroscopy

I
I
S
S
xx
x x x
t1t1
mm
tt22
And the resulting spectrum

I
I
S
S
Cross Peaks tell us about interacting spins.
2D NOESY vs 1D NMR
69 amino acids, M = 7688
2 D NOESY Why?
Advantages wrt 1D 1H{1H} NOE:
Simplification of crowded spectra
No need for selective excitation of individual
resonances
Higher efficiency
NMR in Solids
Problems:
Through Space dipolar coupling not averaged out
Distance dependent information on spin
(broadened spectra)
separations!
Hence, long spin lattice relaxation times T1 (lack of

modulation of dipolar coupling) and therefore restriction
of pulse repetition rate, consequently, poor S/N
Fast spin-spin relaxation times T2 (line broadening)
Chemical Shift anisotropy not averaged out (line
broadening)
Often broad, structureless resonance
Temperature dependence of line

width
Proton resonance line
Solid complex adduct
The Dipolar Coupling-Through

Space Coupling
N
repulsion
attraction
Every nucleus with non-zero I, has a magnetic dipole I

z
Bz
Bx
y
x
0
Bx
3 sin cos
3
4 r
By 0
0
2
Bz
(
3
cos
1)
3
4 r
Anisotropic quantity
In a single crystal, this is simple:

Recall:
( 3 cos 2 1 ) 0 ,ie , 54.7
KAX: splitting in spectrum of X caused by dipolar coupling to A
Magic Angle Spinning

0
2
Bz
(3 cos 1)
3
4 r
=0
for
At this angle all dipolar interactions disappear!
Recall here that the resonance frequency of a given nucleus X

coupled to a nucleus A is determined by the total field it experiences
in z-direction, ie, B0 BAz where BAz is the dipolar field generated
by A on X.
But what about a powder?
Every molecule AX has a unique but different molecules

have different We need a trick.
54.7o
54.7o
A powder sample is mounted for magic angle spinning and

gives the internuclear vectors an average orientation at the
spinning angle.
Also removes chemical shift anisotropy (also follows the
(3cos2-1) law).
How fast can you spin?

- Or the relevance of the
spinning speed.
Assume:
Static line width of resonance to be studied
(ie, undesired interaction) is f Hz then
spinning speed must exceed f Hz if all
broadening interaction are to be nullified.
Spinning speeds of up to 35 kHz possible.
(Ph)331PO
per
par
static
1.9kHz
Typical spectrum of a system

with axial chemical shift
anisotropy.
At low spinning rates,
observation of side bands (info
about principal components of
shielding tensor).
3.8kHz
At high spinning rate we see a

single resonance at isotropic
chemical shift.
iso
CP-MAS 15N spectrum of

(NH4)NO3 CPMAS
The CP(Cross polarisation)-MAS (Magic Angle Spinning) 15N spectrum

of NH4NO3 shows two interesting effects:
1) the bigger chemical shift anisotropy for NO3- as compared with NH4+
2) the greater intensity for NH4+ due to magnetisation transfer from 1H.
2Ca(CH3CO2)2.H2O
M o d u la t io n D e p t h
Electron Paramagnetic
Resonance (EPR)
=
Electron Spin
Resonance (ESR)
1
0 .9 5
0 .9
0 .8 5
0
0 .5
T im e / s
1 .5

ENDOR at 275 GHz
(Schmidt et al 2005).
The HIPER project

Bringing the NMR
paradigm to ESR
Graham Smith et al.
Mbius & coworkers 360GHz
EPR is developing fast

because its APPLICATIONS
so demand
E R samples
Paramagnetic
Most substances do not contain paramagnetic species
and are hence EPR silent
Advantage
1) Easier to interpret
2) Introduction of Spin Spies
Disadvantage
Fewer accessible systems
a)
S
N
O
b)
O
H2N
+ Protein-SH
S
S
N
Protein
OH
Applications of EPR
Study of Electron Transfer Processes
Applications of EPR
Study of N@C60 (and others)
Quantum Computing
Phase transition temp: 260K
4
S3/2
(14N) = 1
FT-EPR
K.P. Dinse
Local Structure
ENDOR/ESEEM in proteins
Applications of EPR
Long range structure

Use of Spin Labels
Light Harvesting complexes
Energy Splittings and Selection Rule

ES= +mSgeBB0
cf.
EI = - mIhB0
mS=1 -eh = geB
(nucleus)
H frequency/MHz
200
400
mS = +1/2
B0/T
10
20
mS = -1/2
Q
X
W
100
300
ESR frequency/GHz
The g-value
The g-value is a unique property of the molecule as a whole and

independent of any electron nuclear hyperfine interactions.
E = mSgeBB0
ge
In case the electron
is the only source of
magnetism in the
sample
E = mSgBB0
SO coupling (SO constant )
leads to derivation of g from that
of free electron
n
g
Ees E gs
When unpaired electron couples to

1) Empty orbital (e.g., d1), g<ge
2) Occupied orbital (e.g., d9), g>ge
h
(GHz )
g
0.07145
B B
B (T )
For most organic radicals, g ge
For transition metals, large deviations from ge
possible
g can be measure to high accuracy (0.0001)
g is the chemical shift of NMR
g depends on structure of radical, excitation energies,
strengths of spin-orbit couplings
Note: later, we will discuss that g is anisotropic and not actually a scalar but a tensor.
Isotropic Coupling between an electron

and a nuclear spin 1/2
S in field
Hyperfine Coupling
I in field
S I
I
SI
aiso/4
aiso/4
S
S
I
SI
(mS , mI ) mS S mI I mS mI aiso
mS 1, mI 0
aiso/4
SI
aiso/4
|aiso|
S
More than one nucleus
1 spin nucleus
SI
SI
Sb
Sb
2 spin nuclei
SI1I2
SI1I2
SI1I2
SI1I2
SI1I2
SI1I2
SI1I2
SI1I2
(mI ) S mI aiso
3 spin nuclei
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
Allowed Transitions for N nuclei

with spins Ik
N nuclei couple to S
Total Number of states:
2 (2 I k 1)
k
Total number of allowed transitions
ne (2 I k 1)
k
Frequencies of allowed transitions
(mI ) S mI aiso
The EPR signal is typically in

the first derivative form
Employ modulation technique
EPR of a Simple Isotropic Ccentred radical

1mT
Another isotropic system in

-.
solution: BH3
EPR spectrum of [BH3] in
solution. The stick diagram
marks the resonances for the
11
B(I=3/2) and the three protons.
The remaining weak
resonances are due to the
radicals containing 10B(I=3).
Oxidation of a Chromium (III) porphyrine

derivative* (still, isotropic in solution)
S(Cr5+) = 1/2
I(14N) = 1
I(53Cr) = 3/2 (9.6% abundant)
But nothing is ever that simple

Anisotropic Interactions (of significance in solids,

frozen solutions, membranes etc.)
with the applied field
with surrounding magnetic nuclei
between electron spins (if more than one, obviously)
Recall:
Description of physical quantities
Isotropic:
Directional:
Interactions between vectorial quantities:
scalars
vectors
tensors
g is anisotropic and varies with

direction
g 'x'x' g 'x' y ' g 'x'z '

g ' y 'x' g ' y ' y ' g ' y 'z '
g 'z 'x' g 'z ' y ' g 'z 'z '
where
g 'ij g ' ji
Diagonalise
g xxx
g yyy
g zzz
Principal values
Anisotropy:
g iso 1 ( g xx g yy g zz )
3
g g zz g iso
Asymmetry:
( g zz g xx )
Isotropic g:
For an arbitrary orientation of

a crystal in a magnetic field
In spherical coordinates:
g ( g sin cos
2
xx
g sin sin
2
yy
g cos )
2
zz
1/ 2
And the resulting powder

spectrum for a rhombic g-tensor
Low spin Fe3+ in
cytochrome P450
Powder
spectrum
1st derivative
g xx
g yy
g zz
Often the g tensor has axial

symmetry
Then:
g g zz
g g xx g yy
And:
g ( g sin g cos )
2
1/ 2
ESR spectrum of a simple d

system
g
But things are not that easy
The hyperfine couplings can also be anisotropic (and

often are!)
A Aiso Adipolar
Recall:
Fermi contact Interaction
(discussion of J)
Density of unpaired electron at
nucleus (s-orbital character in
SOMO)
ISOTROPIC
Recall:
Dipolar Interaction, D
p,d,f orbital character in
SOMO
Averages out in solution
ANISOTROPIC
A Model Cu system
2+
Axial symmetry
I(65Cu) = 3/2 d9, S=1/2
Li ( CO2 )
+ 13
I(13C) = , I(7Li) = 3/2
12
A(13C)>>A(7Li): Spin density mainly on 13C
Transition Metal EPR

Complicated by the fact that transition metal systems might
have several unpaired electrons and several approximately
degenerate orbitals
3d elements important as only moderate spin-orbit coupling
Ability to distinguish between high spin and low spin
complexes (in ligand fields): coordination number and
geometry accessible via EPR
Difficult to observe EPR on systems with integer S
Systems:
Ti3+(d1)S=1/2
Fe3+(d5) S=5/2 (high spin) often high anisotropy, S=1/2 (low spin)
Cu2+(d9) S=1/2 I=3/2 for 63Cu and 65Cu
Co2+(d7) S= 3/2 (high spin) S=1/2 (low spin)
Multiple Resonance Techniques
EPR spectrum of the phenalenyl radical
The problems of resolving the hyperfine lines may be

linked to that of a man with several telephones on his desk
all of which ring at the same time. If he tries to answer them
all, he hears a jumble of conversations as all callers speak
to him at once. Of course his callers have no problem
they only hear one voice.
This is analogous to recognising

that each nucleus experiences the hyperfine field of only
one electron.
Each (spin-1/2) nucleus then gives rise to two resonance
conditions depending on whether the electron hyperfine field
opposes or augments the applied field.
How?
A strong radiofrequency (NMR) field induces NMR
transitions which are observed as a change in the intensity
of an electron resonance condition.
Electron Nuclear Double Resonance (ENDOR)
Electron Nuclear Double Resonance
Isotropic Coupling between an electron

and a nuclear spin 1/2
Recall:
S I
aiso/4
aiso/4
I
SI
S
S
S
SI
aiso/4
SI
aiso/4
The ENDOR experiment (simplified)

NMR transition(3-4) at
1
I a
2
Recall:
1
1
1
E4 s I a
2
2
4
1
1
1
E3 s I a
2
2
4
4
3
| S I
| S I
Thermal EPR 1-3

Equil. saturated.
1
1
1
1
sat
1
1
1
E2 s I a
2
2
4
1
1
1
E1 s I a
2
2
4
| S I
| S I
Previous overhead
Relative populations are given by Boltzmann at thermal equilibrium
(I<<S, hence populations of 1 & 2, 3 & 4 assumed identical)
Irradiate 1-3 transition (saturate at high power) same
populations in 1&3 now
Irradiate system with RF (NMR) and sweep frequency whilst
continually saturating EPR transition; observe the intensity of its
absorption
When RF frequency matches |I-a/2|, transition 3-4 will be
induced, restoring some population difference between levels
1&3
More EPR absorption now possible this is an ENDOR signal
Equally, when RF frequency matches |I + a/2| (1-4 transition), this
time a pumping from 1-4 occurs (as 4 has the higher population)
and a population difference between 1&3 is again achieved and
EPR transition enhance the second ENDOR signal
In practice, need to consider spin lattice relaxation processes
Tetracene cations in sulphuric acid
EPR spectrum
ENDOR
Orientation Selection
EPR
Hyperfine
couplings not
resolved
1
H ENDOR
Toluene Solvent
Two wide doublets which give the hyperfine couplings

to protons in the C8H8 and C5H5 rings directly. Repeat
for parallel components and find spin densities.

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Physical Methods in Inorganic Chemistry Magnetic Resonance: Lecture Course Outline Lecture 1: A Quick Reminder

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Physical Methods in Inorganic Chemistry

Lecture Course Outline

NMR Methods continued 2D and others

Electron Paramagnetic Resonance

Physical Methods Magnetic Resonance