CM2133

Foundations of Physical Chemistry

Lectures 9 & 10
Assoc. Prof. Tan Zhi Kuang
[email protected]
6516-6776
Spin Resonance
Spectroscopy
Key Concepts
1. To describe the origins of spin resonance
2. To describe the principles of nuclear magnetic
resonance (NMR) spectroscopy MRI principles
uses same as nmr

3. To determine molecular structures using NMR

spectroscopy
4. To describe the basic principles of electron
paramagnetic resonance (EPR) spectroscopy
electron version of urr.
 Nuclear Spin
• Protons and neutrons in the atomic nucleus
𝟏𝟏 𝟏𝟏
possess spin of + or − , similar to electrons
𝟐𝟐 𝟐𝟐 Similar too
-

• Spins may pair up and cancel out

• Nuclear spin magnetic quantum number is
denoted as 𝒎𝒎𝑰𝑰 behaves spinning like it is
but it
• Most important nuclear spin for chemical does not
𝟏𝟏 anually
analysis is 𝑯𝑯 (only 1 proton in nucleus) spin
JU4 9

mather at 11al
Number of Number of Spin quantum
Examples experiment
protons Neutrons number a
Even Even 0 12
𝐶𝐶, 16𝑂𝑂, 32𝑆𝑆
odd A spinning charge
Odd 7 Even
⑧ 1/2 𝟏𝟏
𝑯𝑯, 𝟏𝟏𝟏𝟏 𝟑𝟑𝟏𝟏
𝑭𝑭, 𝑷𝑷
Odd Even 3/2
↑ 11
𝐵𝐵, 35𝐶𝐶𝐶𝐶, 79𝐵𝐵𝐵𝐵
creates magnetic
field, like a current V

0 𝟏𝟏𝟑𝟑
SimMV
Even 3 Odd 1/2 𝑪𝑪
to protoUNMR

Even Odd 3/2 127

𝐼𝐼 flowing through a
Even Odd 5/2 17
𝑂𝑂
* coil in a solenoid
W canabsor by empirical observations

Odd Odd spin an

tUAUSHOU 1 levlt 2
𝐻𝐻, 14𝑁𝑁 to measure espin
radIO
waves
Nuclear Spin in Magnetic Field
Zeeman Effect
• Presence of an external
magnetic field causes the
two opposite spin states to
have different energies
• Alignment of spin magnetic
dipole with external field has
lower energy and alignment
against has higher energy

Magnetic field
lines point field
from North to aligned
• The stronger the external South outside
magnetic field, the larger the magnet, and
difference opposite inside
splitting of energy levels larger
between the two spin states
– Zeeman Effect
 Nuclear Spin in Magnetic Field
Precession and Larmor Frequency
nee
- 𝑩𝑩
• In the presence of an external magnetic field,
the magnetic dipole from the spinning nucleus
tries to align with the external field
• The inward alignment force (torque) causes
the spinning nucleus to precess around the
Source: xrayphysics.com
direction of the external field
• The frequency of precession (𝝂𝝂) is known as 𝑩𝑩
Larmor frequency and is given by the equation
(precession frequency
magnelogy's
-
~extfield where 𝑩𝑩 is the external
ratIO i

crelated to 𝜸𝜸𝑩𝑩 in t magnetic field (in Tesla, 𝑇𝑇)

𝝂𝝂
magnetic = and 𝜸𝜸 is the magnetogyric
alpole moment
funnels
𝟐𝟐𝝅𝝅 ratio (in 𝐵𝐵𝑟𝑟𝑟𝑟 𝑠𝑠 −1 𝑇𝑇 −1 )

Larmor frequency (related to the magnetic

Sinherent properlynucleus.
of
dipole moment of nucleus)
Principles of Nuclear Magnetic Resonance Spectroscopy
whatwe care aboutis the precession
NMR Spectroscopy
• When irradiated with radiowaves
with a frequency equal to the Larmor
frequency, energy is absorbed to 𝟏𝟏 absorption
− puOtOU
excite nucleus to higher energy spin 𝟐𝟐
rad 10

state – resonance occurs waves

• Relaxation back to lower energy spin

state causes radiowave emission –
𝟏𝟏
detected to give NMR spectrum NMR + emission
t 𝟐𝟐
energy larmofennency

O
gap 𝜸𝜸𝑩𝑩𝒉𝒉
0=
∆𝑬𝑬 = 𝒉𝒉𝝂𝝂 EPR
𝟐𝟐𝝅𝝅
Selection Rule
• The nuclear spin magnetic
quantum number can
change by one (∆𝒎𝒎𝑰𝑰 = ±𝟏𝟏)
Principles of Nuclear Magnetic Resonance Spectroscopy
NMR Spectroscopy
• When irradiated with radiowaves
with a frequency equal to the Larmor
frequency, energy is absorbed to 𝟏𝟏 absorption
−
excite nucleus to higher energy spin 𝟐𝟐
state – resonance occurs
• Relaxation back to lower energy spin
state causes radiowave emission –
𝟏𝟏
~doesspectrum
detected to give NMR interfere because
not diff
+
𝟐𝟐
emission

𝜸𝜸𝑩𝑩𝒉𝒉
∆𝑬𝑬 = 𝒉𝒉𝝂𝝂 =
𝟐𝟐𝝅𝝅
Selection Rule
• The nuclear spin magnetic
quantum number can
change by one (∆𝒎𝒎𝑰𝑰 = ±𝟏𝟏)
 Shielding
The resonance frequency of 1H (proton) can be slightly different due to
their different chemical environment ver righthand grip will
• The applied external magnetic field induces the electron cloud around the proton
to circulate, creating a small local field that opposes the external field
• The net magnetic field experienced by the nucleus is reduced – known as shielding
• Protons with different chemical environment has different electron cloud density
• Protons with higher electron density – shielded – lower resonance frequency
• Protons with lower electron density – deshielded – higher resonance frequency
• Protons with different shielding gives different peaks in the NMR spectrum
nextto ele Groveg
element
-
ercloud withdrawn

t
desniended

O
pro+Oy
d 𝜸𝜸𝑩𝑩
higher us Electron is negative, 𝝂𝝂 =
+19 hence direction of 𝟐𝟐𝝅𝝅
esiegeis
magnetic dipole is
opposite
Chemical Shift
The NMR spectrum does not show absolute resonance frequency, but
shows the shift in resonance frequency with respect to a reference mielded
protons highly
compound – tetramethylsilane (TMS)
I reference po High electron
LOW fred
density protons
applied free:natural frequency
Reso: ↓
as precession (highly-shielded) g

(lowest soften
same donate e-
applying photonfrey:
rich -
Heg noud
• The shift in resonance frequency is given in parts-per-million (ppm) and
is known as chemical shift (𝜹𝜹) Shiftinf WH TMS
for differentnur

difference
high. - ~low machines chemical
𝝂𝝂 − 𝝂𝝂𝑻𝑻𝑻𝑻𝑻𝑻
O
if different
between 𝜹𝜹 = × 𝟏𝟏𝟏𝟏𝟔𝟔 62 if th are

usually be
tre (in ppm) 𝝂𝝂𝑻𝑻𝑻𝑻𝑻𝑻
Fraction
• Chemical shift (in ppm) is unaffected by external magnetic field strength
(factor cancels out in numerator and denominator) and always has the
same value for the same molecule regardless of the magnet used
• The unique chemical shifts given by the chemical environment of the
protons makes NMR one of the most powerful techniques in chemical
structure analysis and identification
Chemical Shift
The NMR spectrum does not show absolute resonance frequency, but
shows the shift in resonance frequency with respect to a reference
compound – tetramethylsilane (TMS)
High electron
density protons
(highly-shielded)

• The shift in resonance frequency is given in parts-per-million

under (ppm) and
is known as chemical shift (𝜹𝜹) aven
wine
intensity
𝝂𝝂 − 𝝂𝝂𝑻𝑻𝑻𝑻𝑻𝑻 directly to
peak
𝜹𝜹 = × 𝟏𝟏𝟏𝟏𝟔𝟔 proportional in
(in ppm) 𝝂𝝂𝑻𝑻𝑻𝑻𝑻𝑻 proton
of
nO
samer enviro
memical field strength
• Chemical shift (in ppm) is unaffected by external magnetic
(factor cancels out in numerator and denominator) and always has the
same value for the same molecule regardless of the magnet used
• The unique chemical shifts given by the chemical environment of the
protons makes NMR one of the most powerful techniques in chemical
structure analysis and identification
Intensity of Resonance Signal
The area under each set of peaks (obtained by integration) is proportional
to the number of chemically equivalent protons responsible for the peaks
• By integrating each set of peaks, the ratio of protons can be determined

curve nor
to

aven
under
proportionalproton
alvery

not perfect
spectroscopy
is
+- 2

+
~ enor

add
Proton
Ratio 2 : 3 : 3
 Fine Structure of Resonance Signals
Chemically non-equivalent protons on adjacent carbons (1H 3 bonds apart)
can cause the splitting of the NMR peak due to spin-spin coupling
• Magnetic field from neighbouring spinning nuclei can be added to the external field
and cause a higher resonance frequency (higher chemical shift)
• Magnetic field from neighbouring nuclei in opposite direction can be subtracted
from the external field and cause a lower resonance frequency (lower chemical shift)
• This spin-spin coupling causes the NMR peaks of Br2CHCHCl2 to split into two sets of
doublets
o
Amprotons cause splitting
sbondapdr
on now reghbour is splitting
depending

I sightly higher memical mist

O
nupier
 Spin-Spin Coupling
Spin-spin coupling for cases with more than 1 neighbouring protons
econfiguers

Note:
• Spin-spin coupling for 1H NMR is only observed between chemically
non-equivalent protons 3 bonds apart (2 and 4 possible, but rare)
• Spin-spin coupling between chemically equivalent protons is not
observed (forbidden transitions)
-
Multiplicity
The number of peaks caused by spin-spin coupling is called
the multiplicity of the signal
• Multiplicity follows the ‘𝑵𝑵 + 𝟏𝟏 rule’, where 𝑵𝑵 is the
number of neighbouring protons causing the splitting
• The intensity ratio of the split peaks follows the Pascal’s
triangle
 Coupling Constants
le4Ure 709,18
11
~Splitting
Spin-spin coupling can be quantified by the coupling constant (𝑱𝑱) -I

• Spin-spin coupling (splitting of peak) is

nee Split in chemical shift
convert intopari

due to magnetic influence from the spin of ↑

(in ppm) how
big is
egaplnppon
neighboring 1H (not from external B field)
how I with
~ I
couple NMR Frequency (in Hz)
• The extent of coupling is thus the same for my neighbour ∆𝜹𝜹 × 𝝂𝝂𝟏𝟏
HOW (may take 𝝂𝝂𝑻𝑻𝑻𝑻𝑻𝑻 )
𝑱𝑱 =
Is

the same set of protons regardless of the

Convening
my rgnsour into

𝟏𝟏𝟏𝟏𝟔𝟔 convertpart
of of
will moleculesame
NMR machine used – coupling constant (in conple (in Hz) W
may
be

Hz) is independent of external B field I

chemical shifts back + of
frequency tO
Wrt
6 Hz 6 Hz 6 Hz
• The coupling constant is mutually equal TMS

I
for the protons coupling with each other
(HA causes same amount of splitting to HX
as HX causes to HA) – good for identifying amountis
finding out
neighboring pairs how big is egap in ppm

Coupling constants for various proton pairs

H H R H H H H R H H H H H
R R
R
R R H R R R H R R O
~ona
H
alkane vinylic trans vinylic cis vinylic geminal ortho-benzylic meta-benzylic aldehyde
J = 6-8 Hz J = 11-18 Hz J = 6-15 Hz J = 0-5 Hz J = 6-10 Hz J = 0-4 Hz J = 2-3 Hz
 NMR Methods
• A sample dissolved in deuterated solvent is placed within a strong Nuclear magnetic
superconducting electromagnet resonance spectroscopy
• Homogeneity of the magnetic field around the sample is improved by
adjusting the current in small coils - shimming Superconducting
electromagnet
• A short pulse of radiowaves with a broad range of frequencies is sent
towards the sample to excite the nuclear spin transitions – causes spin
‘flip’
• The relaxation back to the lower energy spin state emits radiowaves
that is detected by a coil around the sample
• The emitted radiowave signal is known as the free induction decay
(FID), and contains a sum of all emitted radiowave frequencies
• NMR spectrometer is usually defined by the radiowave frequency used
(300 MHz, 500 MHz), which is related to the strength of the magnet
magnetic Receive by a
proportional
to Source: Bruker
f divertly
↳

big magnets detector coll

crosserllonal view of
machine
𝜸𝜸𝑩𝑩
delaying in intensity 𝝂𝝂 = Radiowave
𝟐𝟐𝝅𝝅 Wil

magnetic
field homogenous
-
same splitting
sharp peak

Free induction decay (FID)

 NMR Methods
• A sample dissolved in deuterated solvent is placed within a strong Nuclear magnetic
superconducting electromagnet low reso Image
resonance spectroscopy
• Homogeneity of the magnetic field around the sample is improved by
adjusting the current in small coils - shimming Superconducting
electromagnet
• A short pulse of radiowaves with a broad range of frequencies is sent
towards the sample to excite the nuclear spin transitions – causes spin
out
ca
‘flip’ will can

• The relaxation back to the lower energy spin state emits radiowaves
that is detected by a coil around the sample
• The emitted radiowave signal is known as the free induction decay
(FID), and contains a sum of all emitted radiowave frequencies
• NMR spectrometer is usually defined by the radiowave frequency used
(300 MHz, 500 MHz), which is related to the strength of the magnet
measured
f
every single
be Source: Bruker
will Hill
𝜸𝜸𝑩𝑩 uso photo.
𝝂𝝂 = high noticably
douplet
𝟐𝟐𝝅𝝅 smaller

0
Free induction decay (FID)
 NMR Methods
• A sample dissolved in deuterated solvent is placed within a strong Nuclear magnetic
superconducting electromagnet resonance spectroscopy
• Homogeneity of the magnetic field around the sample is improved by
adjusting the current in small coils - shimming Superconducting
electromagnet
• A short pulse of radiowaves with a broad range of frequencies is sent
towards the sample to excite the nuclear spin transitions – causes spin
‘flip’
• The relaxation back to the lower energy spin state emits radiowaves
that is detected by a coil around the sample
• The emitted radiowave signal is known as the free induction decay
(FID), and contains a sum of all emitted radiowave frequencies
• NMR spectrometer is usually defined by the radiowave frequency used
(300 MHz, 500 MHz), which is related to the strength of the magnet
noke lower signal larger men you unden energy gap Source: Bruker
dUO tO b8HEmann diGribUtIOn
𝜸𝜸𝑩𝑩 I
𝝂𝝂 =simple samples ↓
canttellapat triplets
𝟐𝟐𝝅𝝅

biological
A sampled
especially 88 telldI4In4lY
matzounare

Free induction decay (FID)

 Fourier Transform NMR
Free induction decay (FID) NMR Spectrum
& sind
rm
splitting war

amplitude
usive

⑧ Fourier
transform

Chemical shift (ppm)

• Fourier transform breaks the
free induction decay (sum of
radiowaves) into individual
sine waves, each with their Amplitude
own frequency and amplitude
• The amplitude vs. frequency
(chemical shift) is plotted to
give the NMR spectrum axid
time is ex
 The Fourier Series (Time Domain)
(main difference converting asignal into vertz

Any waveform or function is a sum of sine and cosine waves with

different amplitude and frequency
Maanber1,2,3,4,5,6
math same butaxis changed ∞ ~ ∞

8
2𝜋𝜋𝜋𝜋𝑡𝑡 2𝜋𝜋𝑠𝑠𝑡𝑡
𝑓𝑓 𝑡𝑡 = 𝐴𝐴0 + � 𝐴𝐴𝑚𝑚 𝑐𝑐𝑐𝑐𝑠𝑠
funtion
oftime
𝑚𝑚=1I 𝑇𝑇
period - 0
+ � 𝐵𝐵𝑛𝑛 𝑠𝑠𝑠𝑠𝑠𝑠
𝑇𝑇
𝑛𝑛=1
interns
Frave no
frequency
𝒎𝒎 𝒏𝒏
where and are frequencies of the respective cosine and sine waves
𝑻𝑻 𝑻𝑻

The amplitude for each sine or cosine wave with their respective
frequency can be found by the equations below
𝑇𝑇
2 2𝜋𝜋𝜋𝜋𝑡𝑡
𝐴𝐴𝑚𝑚 = � 𝑓𝑓 𝑡𝑡 𝑐𝑐𝑐𝑐𝑠𝑠 𝑟𝑟𝑡𝑡
𝑇𝑇 𝑇𝑇 𝑇𝑇
1 0
𝐴𝐴0 = � 𝑓𝑓 𝑡𝑡 𝑟𝑟𝑡𝑡 𝑇𝑇
𝑇𝑇
0 2 2𝜋𝜋𝑠𝑠𝑡𝑡
𝐵𝐵𝑛𝑛 = � 𝑓𝑓 𝑡𝑡 𝑠𝑠𝑠𝑠𝑠𝑠 𝑟𝑟𝑡𝑡
𝑇𝑇 𝑇𝑇
0
 Nuclear Magnetic Resonance Spectrum Analysis
org
me
mod ule
Deshielded – protons close to Shielded – protons close to
electron-withdrawing groups electron-donating groups
no
adjacentHatory

mette,eld

shieldedIOWer
merical shift 𝜸𝜸𝑩𝑩
Increasing Larmor frequency deshielded
chemical 𝝂𝝂 =
& radiowave frequency
higher
mift 𝟐𝟐𝝅𝝅
Position of NMR Signals
labile proton?
5
guideline for
identifying protons

not beside
dentroreg
e-rich
shielded

aidenpea magnetic anxotropic

deshielded
eff
~halogen
2
er
withdraw
cond
deshielded

Source: Ian Hunt, McGraw-Hill

Magnetic Anisotropy
π electrons circulate and form a ring current under an external magnetic
field, creating a local field that opposes the external field within the ring
Copport applied field
Benzene B Alkene B Aldehyde B
add on to eoriginal
H H magnetic field
to H H H
↑
A
chemical
H H high O
shift
H H H
smaller than benzene
H H
&direction of deshield
-> 𝛿𝛿 = 6.5 − 8 𝑝𝑝𝑝𝑝𝜋𝜋 mayne proton 𝛿𝛿 = 4.5 − 7 𝑝𝑝𝑝𝑝𝜋𝜋 not as
but

strong as benzene
𝛿𝛿 = 9 − 10 𝑝𝑝𝑝𝑝𝜋𝜋
Outside the ring current, the local field is in the same direction as the external field, causing outside
protons to experience higher net field and possess higher resonance frequency and chemical shift
The solenoid shows
Alkyne conventional current
alkene does nothave B
e
For alkyne, the protons
H (flow of positive charge)

Er experience a local field that

is in an opposite direction to The π ring current shows
⑧negates
G
the external field, hence flow of electrons that

winferent
giving a lower resonance are negative, hence
H b frequency and chemical shift direction of magnetic
en
𝛿𝛿 = 2 − 3 𝑝𝑝𝑝𝑝𝜋𝜋 dipole is opposite
Magnetic Anisotropy
π electrons circulate and form a ring current under an external magnetic
field, creating a local field that opposes the external field within the ring
Benzene B Alkene B Aldehyde B
H H
H H H
H H O
H H H

H H
𝛿𝛿 = 6.5 − 8 𝑝𝑝𝑝𝑝𝜋𝜋 𝛿𝛿 = 4.5 − 7 𝑝𝑝𝑝𝑝𝜋𝜋 𝛿𝛿 = 9 − 10 𝑝𝑝𝑝𝑝𝜋𝜋
Outside the ring current, the local field is in the same direction as the external field, causing outside
protons to experience higher net field and possess higher resonance frequency and chemical shift
The solenoid shows
Alkyne conventional current
B For alkyne, the protons
H (flow of positive charge)
experience a local field that
is in an opposite direction to The π ring current shows
the external field, hence flow of electrons that
giving a lower resonance are negative, hence
H frequency and chemical shift direction of magnetic
𝛿𝛿 = 2 − 3 𝑝𝑝𝑝𝑝𝜋𝜋 dipole is opposite
Hydrogen Bonding
Alcohols, Amines & Amides
O
H H
R
OH
R
N
R R N
R δ−
H
δ+ O
• Protons that are involved in intermolecular R
hydrogen bonding have a large range of chemical R H
O
shifts (𝜹𝜹 = 𝟏𝟏. 𝟓𝟓 − 𝟓𝟓 𝒑𝒑𝒑𝒑𝒎𝒎) δ− hydrogen
• Chemical shift is variable, depending on the extent
bonding
of hydrogen bonding in different solutions and
concentrations
• Higher extent of hydrogen bonding deshields the O
proton and gives a higher chemical shift
• Hydrogen bonded protons cannot be reliably R O H
assigned in NMR spectrum
Carboxylic Acids weakly-bound
O
proton
R OH
• Acidic protons are almost completely stripped of electron density and is
therefore very deshieded (𝜹𝜹 = 𝟏𝟏𝟏𝟏. 𝟓𝟓 − 𝟏𝟏𝟐𝟐 𝒑𝒑𝒑𝒑𝒎𝒎)
 Proton Exchange
Alcohols, Amines, Amides & Acids
• Protons attached to
electronegative oxygen or
nitrogen are slightly labile
H
• The labile protons undergo O
rapid exchange with other H C H
C H Quartet
OH/NH protons or with H
H Singlet
ambient moisture (H2O)
• The labile protons do not stay No spin-spin coupling
on the molecule long enough from OH proton
to cause spin-spin couplingospinspir
e coupling
• The labile protons are effen

typically singlets (sometimes

Chemical shift (ppm)
broad) and do not cause peak
splitting on neighbouring
protons
 Proton Exchange
Alcohols, Amines,
single bond Amides & Acids
can turn

• Protons attached to
electronegative oxygen or
nitrogen are slightly labile
H
• The labile protons undergo O
rapid exchange with other H C H
C H Quartet
OH/NH protons or with H
H Singlet
ambient moisture (H2O)
• The labile protons do not stay No spin-spin coupling
on the molecule long enough from OH proton
to cause spin-spin coupling
• The labile protons are
typically singlets (sometimes
Chemical shift (ppm)
broad) and do not cause peak
splitting on neighbouring
protons
 13C NMR also
spin of
1/2 much weaker NMRagnal -> low abundance
notmuch carbon to generate NMR signal

• 13CNMR signal is much weaker than Deshielded Shielded

1H NMR and does not show spin-spin (electron poor) (electron rich)
coupling between neighbouring
carbons – because of much lower
abundance (1.1%) of 13C dispin pin
can
another
coupung:
130
• 13CNMR reveals number of neighbour morly
but

chemically non-equivalent carbons 12

• Chemical shift of 13C NMR
approximately 20-times of 1H NMR, if
but follow similar trends due to weakness
signal
• Integration of C NMR peaks are
auteten
13

less reliable in predicting number or

ratio of corresponding carbons
abidebet
to
similar get
ridthepeaks
to
But what about coupling of C with H? vin-rpin=
13 1 able

protons try to get

• A radio-frequency pulse can be sent to cause spin-transition in all 1H
𝟏𝟏 𝟏𝟏
• The 1H spin adjacent to the 13C will switch quickly between + and − (averages to 0)
𝟐𝟐 "CNMR 𝟐𝟐 alot ofspin transite
cause in

• It is thus unable to do spin-spin coupling with 13C – known as NMR spin decoupling proton
 Electron Paramagnetic Resonance Spectroscopy
Celeron version ofNMR
𝟏𝟏 𝟏𝟏
• Electrons possess spin of + or −
𝟐𝟐 𝟐𝟐
• Presence of external magnetic field
causes the splitting of energy levels
between the two spin states –
Zeeman Effect 2 spins non-degenerate
• Transitions between the two split
energy levels correspond to
microwave energy – because Zeeman Effect
magnetic moment of electron spin is
much larger than that of nuclear spin
e
bigger furior
g master big,
missaligned − 𝟏𝟏
magnet ∆𝑬𝑬 = 𝒉𝒉𝝂𝝂 = 𝒈𝒈𝝁𝝁𝑩𝑩 𝑩𝑩 magnella3
notmagnet
higher
energy
in
𝟐𝟐
absorption
nucherorderflip microwave est Constant
than
moment
dipole
Bohr
to red
magnetor
where 𝑩𝑩 is the external magnetic field (in Tesla, 𝑇𝑇) zemnt
fe
eff
and 𝝁𝝁𝑩𝑩 is Bohr magneton (9.274 × 10−24 𝐽𝐽 𝑇𝑇 −1 ) iimoune
a lig
ned
and 𝒈𝒈 is factor that is related to the electron not in 𝟏𝟏
environment (𝑔𝑔 = 2.0023 for free electron) more
affected by enviro
not lower +
-rel energy 𝟐𝟐
 Electron Paramagnetic Resonance Spectroscopy
• EPR spectroscopy used to detect not
as useful as NMR

unpaired electrons in organic and

-
inorganic
complexes Imor
radicals and transition metal
molecules not unpaired
do have e-

• Usually, microwave frequency is kept

Source: Bruker
constant and magnetic field is scanned
absorbances per
across a range to achieve resonance ogradient

A
• First derivative of the absorbance d
a
-ofthis graph

commonly recorded as data a gradient

look

• The calculated g-factor may reveal ofabsorbance

graphgradient
information on the environment of *
the unpaired electron
fixed
duemicrone
to

constant
∆𝑬𝑬 = 𝒉𝒉𝝂𝝂 = 𝒈𝒈𝝁𝝁*
𝑩𝑩 𝑩𝑩
 Hyperfine Coupling in EPR Spectroscopy
• Unpaired electron spin couples with neighbouring nuclear
spin to cause splitting of the EPR peak – hyperfine coupling
couple
another form open
spin another proton

• Multiplicity follows the ‘𝑵𝑵 + 𝟏𝟏 rule’, where 𝑵𝑵 is the number

of neighbouring protons causing the splitting – similar to NMR
• The nearer the protons to the radical, the larger the splitting
triplet form less
coupling
n+1 peaks within e
couple
CH3 quartets ↳OO further

e ↳
triplet
H2CLaCH3
away
-sprotom
further
away

3 near protons 2 near protons, 3 far protons

EPR of systems with more than one unpaired electron
is complex and will not be covered in this module