2006 Wolfgang H.

Kramer, Millsaps College

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CD-ORD Spectroscopy
These are called chiroptical methods (techniques): are based on the chirality of a compound

CD: circular dichroism

ORD :optical rotatory dispersion
The nature of polarized light: - light used in UV/VIS spectroscopy is essentially unpolarized
- what happens if you use linearely polarized light?
(sometimes less rigorously referred to as plane-polarized light)

you get information about structural and stereochemical information!!!

What is light?

wave motion propargates in X direction by

transverse vibration. The arrow denotes the
electric field vector at a given instant as the
O light wave progresses along the x-axis
X

Schematic representation of unpolarized and

linearly polarized light. left: cross section of
a narrow beam of ordinary light travenling
directly toward the observer. vibration of the
light may be in any direction that is
perpendicular to the direction of travel

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X linearely and horizontally

linearely and vertically

left circularly

right circularly

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Circularly polarized light: - the transverse vibrations trace out a helix as a function of time
- observer on the x-axis looking toward light source sees the
transverse vibrations like a circle

right and left circulary polarized light:

electrical field vector traces out a right or left handed helical pattern

how does the electrical field vector turn?

if the helix would turn (spinning at you) the field vector would stay at the
same position and not make a circle
so, better: do not turn helix, just push it, then the field vector turns

spin

X X

spinning the helix does not influence the field vector

push
X
X

pushing the helix spins the field vector

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 2006 Wolfgang H. Kramer, Millsaps College
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early 19th century: french physicist Biot and Fresnel found that certain organic compounds
possessed the unusual property of rotating the plane of polarization of
a linearly polarized incident light beam

1817: found out that the extent of optical rotation of a compound increases as one used
light increasingly shorter wavelengths for the measurement
the change in optical rotation with wavelength is termed
optical rotatory dispersion (ORD)

thirty years later: Haidenger: reported observations on the differences in the absorption
of left- and right-handed components of circularly polarized
light
differential absorption of left-and right-handed circularly
polarized light is termed circular dichroism (CD)

both involve optical measurements on chiral molecules

chiroptical methods

CD and ORD are similar to UV/VIS spectrocopy

=> photons are used to excite a compound from the ground state to an excited state
(promote an electron from lower orbital to higher orbital)
=> only difference: UV/VIS uses unpolarized light, CD & ORD used polarized light

Optical Rotation:

observation: the plane of polarized light is turned one way or the other when sent
through a solution of a chiral molecule

how can we understand this?

useful model: consider the linearly polarized light as compared of two oppositely
rotating coherent beams of circularly polarized light
the linearly polarized light is then the vector sum of the left and right
circularly rotating components

vector sum results in properties of linearly polarized light

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 2006 Wolfgang H. Kramer, Millsaps College
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linearely and vertically polarized light E

EL ER
0 E
EL ER

1 2

1
2 4
3 EL ER
4
3 EL ER
5 E

EL ER

okay, now we understand how we have to think, what is now happening when the plane is
turned upon passing through an optically active medium?

when circularly polarized light passes through an optically active medium, the refractive
index (n) for one circularly polarized light component is different from that for the other
the medium is said to be birefringent
n L - nR = 0

differences in refractive indices correspont to differences in light velocities

one of the circularly polarized components becomes retarded with respect

to the other

the two components are no longer in phase

the resultant vector has been rotated by the angle α to the original plane of
polarization

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Representation of linearly polarized light

as a vector sum of two oppositely
x rotating beams of circularly polarized
1
2 x' radiation E L and E R. When the light
α passes through a medium where the
3
4 vector of the left beam lags behind that
5 for the right circularly polarized light,
the plane of the linearly polarized light is
turned.

EL ER
EL E ER 4 5
EL ER

1 2 3 EL ER
E
1 EL ER

E
R
L
L
L
R L 5
4
R L

1 2 3 R
L
R R

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 2006 Wolfgang H. Kramer, Millsaps College
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What is happening in the region of an UV/VIS-absorption band?

the two circularly polarized components in addition to differential retardation because

of birefringence are also absorbed to different extents

in other words: the optically active medium has an unequal molar absorption
coefficient ε for left and right circularly polarized light

this difference in molar absortivity is termed circular dichroism

∆ε = εL − εR = 0

α X'
θ
b
EL

elliptically polarized light:

caused by unequal speed and
unequal absorption of left and
right circularly plarized light

ER

the tangent of the ratio of the

minor axis a to the major axis b
is θ, the angle of ellipticity

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ORD and CD Spectra:

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At the right is a CD spectrum of a decapeptide depicting chloroform–methanol

titrations. Ratios represent concentration of chloroform to that of methanol.
According to Protein Engineering, 15, 331-335 (2002):
"A CD band is observed at 320 nm that also changes sign with change in solvent. One
reason for this band at 320 nm may be the weak electronic transition polarized along
the short axis of the benzene ring. This contribution to the CD spectrum suggests
that the benzene rings are not free to rotate, as expected, owing to the presence of
the side chain C=C double bond.

Its strong intensity also indicates that the phenyl rings are restricted to a preferred
chiral disposition. However, there may be another explanation for the presence of the
CD band at 320 nm. It is known that the dipole–dipole interaction between the
transition moments polarized along the long axis of the chromophores leads to the CD
couplet characterized by the positive band at 260 nm and the negative band at 290
nm, for a right-handed helix.

Similarly, the dipole–dipole interaction between transition moments polarized along the
short axis may lead to a second couplet with a negative band at 290 nm, overlapping
with the previous negative band and a positive band at 320 nm. It may also be that
both of these factors contribute to the presence of the band at 320 nm."

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 2006 Wolfgang H. Kramer, Millsaps College
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difference in CD and ORD spectra:

ORD: involves measurements of a rotation

CD : involves measurements of an absorption, namely the differential absorption of

left- and right-handed circularly polarized radiation

CD occurs only in the vicinity of an absorption band

ORD is theoretically finite everywhere

shape and appearance of CD spectrum closely resembles that of the ordinary UV/VIS
absorption curve of the electric transition to which it corresponds

Unlike ordinary absorption curves, CD curves maybe positive or negative.

CD curves plot ∆ε (or [Θ]) vs. wavelength.
They are difference spectra representing the difference in absorption of left- and
right circulary polarized light, hence the signed nature of the curve.
Each CD curve for each electronic transition also represents a positive or negative
Cotton effect for the transtion.
For every Cotton effect there exists a coresponding ORD effect of the same sign.

∆ε positive Cotton effect

(+) (+) [φ]
corresponding ORD
curve
λ0
λ0

(-) corresponding ORD (-)

curve
[φ] ∆ε
negative Cotton effect

the wavelength λ 0 at the sign change cross-over point of the ORD curve
corresponds to the λ max of the CD curve
.

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 2006 Wolfgang H. Kramer, Millsaps College
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4 Peak
ORD curve of a typical
3 Cotton effect saturated ketone
region
2

[φ] x 10 -3
-1 λ 0 = 295 nm

-2

-3 [φ]Peak - [φ]trough
a= (amplitude)
-4 100
trough
-5

250 300 350

ODR spectra : - from long to short wavelength

- rotation increases in that direction, rapidly before absorption maximum

is approached

- before this maximum, rotational values reach a maximum, termed a peak

- then drop drastically, going through zero rotation (λ 0 )

- reach another inflection point, termed a trough

- the the rotation tends to increase again

- in an ideal case (no other absorption bands near the one measured) λ 0
closely corresponds the λ max, the maximum of the absorption band

- vertical distance between the peak and the trough divided by 100 is
termed the amplitude

- if peak precedes the trough on measuring from longer to short

wavelength, the Cotton effect is termed positive
.

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Determination of absolute configuration

O O

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C
O

special rules: - few substituents (-F, -NMe3 , -cyclopropyl) exhibit antioctant behavior
- ketones with an axial α-chloro or α-bromo substituents: Cotton effect
signs are only determined by octant location of halogen, even if most of
the molecule occupies an oppositely signed octant
(called the "axial halo ketone"-rule of Djerassi and Klyne)

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 2006 Wolfgang H. Kramer, Millsaps College
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Example: What is the absolute configuration of (+)-3-methylcyclohexanon when

the molecule exhibits a positive n π * Cotton effect?
O

CH 3

look at conformations: two conformations for each enantiomer

look at the two following conformations (one is R, one is S)

These are the lowest energy conformations, substituent in equatorial position

check S-configuration

check R-configuration

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 2006 Wolfgang H. Kramer, Millsaps College
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Exition Coupling and Exiton Chirality rule

X* X

Y Y*
Potential Energy

X* Y*

X0 Y0

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100

66

CD
33
∆ε
0

33 UV, ε

66
20000

100
15000

10000

5000

200 250 300 350

UV, λ [nm]

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Negative Exciton Chirality Positive Exciton Chirality

1000

500

∆ε 0

- 500

200 300
λ [nm] .

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Examples:

H
HO
2

HO 1

1S , 2 S

H
OH
2
1 OH
H

1R, 2R

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