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CD-ORD Spectroscopy
These are called chiroptical methods (techniques): are based on the chirality of a compound
What is light?
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2006 Wolfgang H. Kramer, Millsaps College
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left circularly
right circularly
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2006 Wolfgang H. Kramer, Millsaps College
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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
electrical field vector traces out a right or left handed helical pattern
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
push
X
X
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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)
chiroptical methods
Optical Rotation:
observation: the plane of polarized light is turned one way or the other when sent
through a solution of a chiral molecule
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
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2006 Wolfgang H. Kramer, Millsaps College
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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
the resultant vector has been rotated by the angle α to the original plane of
polarization
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2006 Wolfgang H. Kramer, Millsaps College
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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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in other words: the optically active medium has an unequal molar absorption
coefficient ε for left and right circularly polarized light
∆ε = εL − εR = 0
α X'
θ
b
EL
ER
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2006 Wolfgang H. Kramer, Millsaps College
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2006 Wolfgang H. Kramer, Millsaps College
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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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shape and appearance of CD spectrum closely resembles that of the ordinary UV/VIS
absorption curve of the electric transition to which it corresponds
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
- 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
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2006 Wolfgang H. Kramer, Millsaps College
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O O
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2006 Wolfgang H. Kramer, Millsaps College
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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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CH 3
check S-configuration
check R-configuration
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2006 Wolfgang H. Kramer, Millsaps College
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X* X
Y Y*
Potential Energy
X* Y*
X0 Y0
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100
66
CD
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∆ε
0
33 UV, ε
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20000
100
15000
10000
5000
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2006 Wolfgang H. Kramer, Millsaps College
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1000
500
∆ε 0
- 500
200 300
λ [nm] .
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2006 Wolfgang H. Kramer, Millsaps College
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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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