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2006 Wolfgang H. Kramer, Millsaps College

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?

 
λ
λ

O

O X
O X

X

O X
   
   
   
1

1

wave motion propargates in X direction by transverse vibration. The arrow denotes the electric field vector at a given instant as the

light wave progresses along the x-axis

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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O X O X
O
X
O
X
. O X O X X X 2 2006 Wolfgang H. Kramer, Millsaps College linearely and

X

X

2

2006 Wolfgang H. Kramer, Millsaps College

. O X O X X X 2 2006 Wolfgang H. Kramer, Millsaps College linearely and
. O X O X X X 2 2006 Wolfgang H. Kramer, Millsaps College linearely and
. O X O X X X 2 2006 Wolfgang H. Kramer, Millsaps College linearely and

linearely and horizontally

linearely and vertically

left circularly
left circularly

right circularly

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2006 Wolfgang H. Kramer, Millsaps College

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

do not turn helix, just push it, then the field vector turns spin X X spinning

spin

X

turn helix, just push it, then the field vector turns spin X X spinning the helix
X
X

spinning the helix does not influence the field vector

spin X X spinning the helix does not influence the field vector push X X pushing

push

spin X X spinning the helix does not influence the field vector push X X pushing

X

X
X

pushing the helix spins the field vector

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2006 Wolfgang H. Kramer, Millsaps College

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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linearely and vertically polarized light

0 1 2 3 4 5
0
1
2
3
4
5

z

2006 Wolfgang H. Kramer, Millsaps College

E E L E R 1
E
E L
E R
1
E E L E R 2
E
E L
E R
2
4 E L E R 3 E L E
4
E L
E R
3
E L
E

E R

5 E L E R E
5
E L
E R
E

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

that for the other the medium is said to be birefringent n L - n R
that for the other the medium is said to be birefringent n L - n R

n L - n R = 0

differences in refractive indices correspont to differences in light velocities

one of the circularly polarized components becomes retarded with respect to the otherindices correspont to differences in light velocities the two components are no longer in phase the

the two components are no longer in phasecomponents becomes retarded with respect to the other the resultant vector has been rotated by the

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

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0 x 1 2 α 3 4 5 z E
0
x
1
2
α
3
4
5
z
E

2006 Wolfgang H. Kramer, Millsaps College

x'

Representation of linearly polarized light as a vector sum of two oppositely

rotating beams of circularly polarized

radiation E L and E R . When the light

passes through a medium where the vector of the left beam lags behind that

for the right circularly polarized light, the plane of the linearly polarized light is turned.

E L E R E E L E R 4 5 E L E R
E L
E R
E
E L
E R
4
5
E L
E R
1
2
E
3
L
E R
E
1
E L
E R
E
R
L
L
L
R
L
4
5
L
R
1
2
R
3
L
R
R

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2006 Wolfgang H. Kramer, Millsaps College

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

of birefringence are also absorbed to different extents in other words: the optically active medium has

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 = ε L − ε R = 0 X α X' θ b E
∆ε = ε L
ε R
= 0
X
α X'
θ
b
E L
E R
a

elliptically polarized light:

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

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:

2006 Wolfgang H. Kramer, Millsaps College

. ORD and CD Spectra: 2006 Wolfgang H. Kramer, Millsaps College 8 .

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2006 Wolfgang H. Kramer, Millsaps College

. 2006 Wolfgang H. Kramer, Millsaps College At the right is a CD spectrum of a

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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difference in CD and ORD spectra:

ORD: involves measurements of a rotation

2006 Wolfgang H. Kramer, Millsaps College

CD : involves measurements of an absorption, namely the differential absorption of left- and right-handed circularly polarized radiation

of left- and right-handed circularly polarized radiation CD occurs only in the vicinity of an absorption

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 λ 0 [φ]
∆ε
λ 0
[φ]

positive Cotton effect

(+) [φ] λ 0 (-) ∆ε
(+)
[φ]
λ 0
(-)
∆ε

corresponding ORD curve

corresponding ORD curve

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

 

5

4

3

2

1

[φ] x 10 -3

 

-1

-2

-3

-4

-5

Peak ORD curve of a typical saturated ketone Cotton effect region λ 0 = 295
Peak
ORD curve of a typical
saturated ketone
Cotton effect
region
λ 0 = 295 nm
-
[φ] Peak
[φ] trough
a =
(amplitude)
100
trough
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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2006 Wolfgang H. Kramer, Millsaps College

Determination of absolute configuration

O O
O
O

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2006 Wolfgang H. Kramer, Millsaps College C O
2006 Wolfgang H. Kramer, Millsaps College
C
O

special rules: - few substituents (-F, -NMe 3 , -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

Example: What is the absolute configuration of (+)-3-methylcyclohexanon when

the molecule exhibits a positive n

O

when the molecule exhibits a positive n O CH 3 π * Cotton effect? look at

CH 3

when the molecule exhibits a positive n O CH 3 π * Cotton effect? look at

π * Cotton effect?

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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Potential Energy

Exition Coupling and Exiton Chirality rule

X * Y
X *
Y

X

X

*

0

Exition Coupling and Exiton Chirality rule X * Y X X * 0 15 2006 Wolfgang

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2006 Wolfgang H. Kramer, Millsaps College

X Y *
X
Y *
Exition Coupling and Exiton Chirality rule X * Y X X * 0 15 2006 Wolfgang

Y *

Y

0

.

100

66

CD 33

∆ε

0

33

66

100

2006 Wolfgang H. Kramer, Millsaps College UV, ε 20000 15000 10000 5000
2006 Wolfgang H. Kramer, Millsaps College
UV, ε
20000
15000
10000
5000

200 250 300

UV, λ [nm]

16

350

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Negative Exciton Chirality

2006 Wolfgang H. Kramer, Millsaps College

Positive Exciton Chirality

Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300
Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300

∆ε

1000

500

0

- 500

Wolfgang H. Kramer, Millsaps College Positive Exciton Chirality ∆ε 1000 500 0 - 500 200 300

200

300 λ [nm]

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Examples:

HO

H

2 1 HO
2
1
HO

H

1S, 2S

H

2 1 OH
2
1 OH

H

1R, 2R

OH

. Examples: HO H 2 1 HO H 1 S , 2 S H 2 1
. Examples: HO H 2 1 HO H 1 S , 2 S H 2 1

2006 Wolfgang H. Kramer, Millsaps College

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