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Muraleedharan
• When there are even number of protons and even number of neutrons in the
nucleus, the net spin is equal to zero.
• When there are odd number of neutrons and odd number of protons in the
nucleus, it will have an integer spin (i.e. 1, 2, 3)
• If the sum of the number of neutrons and the number of protons is odd number,
the nucleus will have a half-integer spin (i.e. 1/2, 3/2, 5/2).
These rules can be summarized in terms of atomic mass and atomic number as shown
below.
Nuclei are charged and those with a net spin would generate a magnetic dipole
along the spin axis. The magnitude of this dipole is given by the nuclear magnetic
moment μ, which is give by
μ = γ I h / 2π ..................................(1)
where I is the spin quantum number (with values ½, 1, 3/2 etc.) and
From equation (2), it is clear that a radiation of frequency ν = γB0/2π possess the
B
right amount of energy to effect a transition from lower energy α state to higher energy β
state. Absorption of energy takes place only with a certain combinations of field strengths
and radio frequencies during which the system is said to be in a state of resonance.
Energy
Spin state I = -1/2 (β )
I = 1/2
Field strength B0
H H
H H H C C Br
H C C Br H H
H H
Due to the magnetic field generated by the circulating electrons, hydrogens which
lie in the plane of the ring experiences a deshielding effect as shown below (A). At the
same time those situated above and below the plane experience shielding, as the
magnetic lines of force are opposite in direction with respect to the applied field. Similar
effect, but to a lesser extent, can be seen in simple olefins (B), aldehydes etc.
Applied
magnetic
field H H
B0
δ 7-8 ppm δ 5-7 ppm
A B
Illustrative examples:
Chemical shift positions of hydrogen atoms which are placed in the shielding and
deshielding zones of aromatic systems are given below.
Outer protons at 6.9-7.3 δ Inner protons 0.00 δ Outer ring protons at 8.14-8.67 δ
H
Outer protons 7.6 δ CH3 protons at -4.25 δ
H
H H H H H H3C
H CH3
H
[14]-annulene
H H Outer protons at ~ 9 δ Ha
H H 2 Hb
Inner protons at ~ -3 δ Ha at -0.3 δ
3
Hb at 5.1 δ
H H H H H1
4 H1 & H7 at 6.4 δ
H H H7
H H H H H2-H6 at 8.5 δ
5 6
H H
H H
[18]-annulene
Antiaromatic systems
Antiaromatic systems are paratropic. That is, they are able to sustain a
paramagnetic ring current, which lead to shielding of outer ring protons and deshielding
of inner protons (opposite to that of aromatic compounds which show diamagnetic
effect). Examples presented below demonstrate the behavior of magnetic nuclei situated
in an antiaromatic environment.
1) At -170oC, inner protons of [12]-annulene comes at ~8 ppm and outer protons comes
at ~6 ppm which is characteristic of antiaromaticity. Above -150oC, all protons are
magnetically equivalent showing conformational flexibility. Above -50oC, it rearranges
to a bicyclic system as shown below.
above -50oC
[12]-annulene
H H
H H in solution
Nonaromatic
[16]-annulene
H3C H3C
CH3 CH3
reduction