Principles of Molecular

Spectroscopy:
Electromagnetic Radiation and
Molecular structure

Nuclear Magnetic Resonance (NMR)

 E = h 

Electromagnetic radiation is absorbed when the

energy of photon corresponds to difference in
energy between two states.
 What Kind of States?

electronic UV-Vis
vibrational infrared
rotational microwave
nuclear spin radiofrequency

NMR is concerned with change in the direction of

spin orientation as the result of the absorption of
radiofrequency radiation.
 The two nuclei that are most useful to
organic chemists are:

H and 13C
1

both have spin = ±1/2

H is 99% at natural abundance

1

13
C is 1.1% at natural abundance
 Nuclear Spin

+ +

A spinning charge, such as the nucleus of 1H

or 13C, generates a magnetic field. The
magnetic field generated by a nucleus of spin
+1/2 is opposite in direction from that
generated by a nucleus of spin –1/2.
The distribution of
nuclear spins is +
random in the
absence of an
external magnetic
field. +

+
+
An external magnetic
field causes nuclear +
magnetic moments to
align parallel and
antiparallel to applied
field. +

+
H0

+
+
There is a slight
excess of nuclear +
magnetic moments
aligned parallel to
the applied field.
+

+
H0

+
+
 Energy Differences Between Nuclear Spin States

E E '

increasing field strength, HZ

no energy difference in absence of magnetic field
proportional to strength of external magnetic field
 Some important relationships in NMR

The frequency of absorbed

electromagnetic radiation
is proportional to

the energy difference between

two nuclear spin states
which is proportional to

the applied magnetic field

 Some important relationships in NMR

Units
The frequency () of absorbed
electromagnetic radiation Hz (s-1)
is proportional to

the energy difference (E)

kJ/mol
between
(kcal/mol)
two nuclear spin states
which is proportional to
tesla (T)
the applied magnetic field (H0)
 Some important relationships in NMR

The frequency of absorbed electromagnetic

radiation is different for different elements,
and for different isotopes of the same element.

For a field strength of H0 = 4.7 T:

1
H absorbs radiation having a frequency
of 200 MHz (200 x 106 s-1)
13
C absorbs radiation having a frequency
of 50.4 MHz (50.4 x 106 s-1)

Compare to 1015 s-1 for electrons; 1013 s-1 for vibrations

 Some important relationships in NMR

The frequency of absorbed electromagnetic

radiation for a particular nucleus (such as 1H or 13C)
depends on the molecular environment of the
nucleus (the electronic environment).

This is why NMR is such a useful tool

for structure determination. The signals of different
protons and carbon atoms in a molecule show
different signals, just like different functional groups
show different signals in the IR.
 Nuclear Shielding
and
1
H Chemical Shifts

What do we mean by "shielding?"

What do we mean by "chemical shift?"
 Shielding

An external magnetic field

affects the motion of the
electrons in a molecule,
inducing a magnetic field
C H
within the molecule.

H0
 Shielding

An external magnetic field

affects the motion of the
electrons in a molecule,
inducing a magnetic field
C H
within the molecule.
The direction of the
induced magnetic field is
opposite to that of the
applied field. H0
 Shielding

The induced field shields

the nuclei (in this case, 13C
and 1H) from the applied
field.
C H
A stronger external field is
needed in order for energy
difference between spin
states to match energy of
rf radiation. H0
 Chemical Shift

Chemical shift is a
measure of the degree to
which a nucleus in a
molecule is shielded.
C H
Protons in different
environments are shielded
to greater or lesser
degrees; they have
different chemical shifts. H0
 Downfield Upfield
Decreased shielding Increased shielding

(CH3)4Si (TMS)

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

H0
Chemical shift (, ppm)
measured relative to TMS
 Cl
 7.28 ppm
H C Cl

Cl

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

H0
Chemical shift (, ppm)
 Effects of Molecular Structure
on
1
H Chemical Shifts

protons in different environments experience

different degrees of shielding and have
different chemical shifts
 Electronegative substituents decrease
the shielding of methyl groups

CH3F  4.3 ppm

CH3OCH3  3.2 ppm
CH3N(CH3)2  2.2 ppm
CH3CH3  0.9 ppm
CH3Si(CH3)3  0.0 ppm CH3OCH3 CH3CH3

10 9 8 7 6 5 4 3 2 1 0

CH3F CH3N(CH3)2 CH3Si(CH3)3

 Effect is cumulative

CHCl3  7.3 ppm

CH2Cl2  5.3 ppm
CH3Cl  3.1 ppm

CHCl3 CH3Cl

10 9 8 7 6 5 4 3 2 1 0

CH2Cl2
Protons attached to sp2 hybridized carbon
are less shielded than those attached
to sp3 hybridized carbon

H
H H H H
H H C C CH3CH3
H H H
 7.3 ppm  0.9 ppm
 5.3 ppm

10 9 8 7 6 5 4 3 2 1 0
 Information contained in an NMR
spectrum includes:

1. number of signals

2. their intensity (as measured by area

under peak)

3. splitting pattern (multiplicity)

We shall not consider spin-spin splitting

 N CCH2OCH3
Number of Signals

protons that have different

OCH3
chemical shifts are chemically

nonequivalent and exist in NCCH2O

chemically different molecular

environments

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
H0
Chemical shift (, ppm)
 1
H and 13C NMR compared:

both give us information about the number of

chemically nonequivalent nuclei (nonequivalent
hydrogens or nonequivalent carbons)

both give us information about the environment of the

nuclei (hybridization state, attached atoms, etc.)
 ClCH2CH2CH2CH2CH3

1H NMR cannot
distinguish two of the CH2
ClCH2 CH3
groups (C2 and C4)
?

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

H
1 H0
Chemical shift (, ppm)
 ClCH2CH2CH2CH2CH3

a separate, distinct
peak appears for
each of the 5 carbons

Solvent
CDCl3

200 180 160 140 120 100 80 60 40 20 0

H0
C
13 Chemical shift (, ppm)
 13
C Chemical shifts are most affected by:

• hybridization state of carbon

• electronegativity of groups attached to carbon

Increasing electronegativity

H0

220 200 180 160 140 120 100 80 60 40 20 0

As the atom attached to a carbon becomes more
electronegative, the carbon atom signal is observed
at lower field

OH
61 23

H0
220 200 180 160 140 120 100 80 60 40 20 0

O
202 138 23

sp2 hybridized carbon is at lower field than sp3