CHIROPTICAL

PROPERTIES

- Sakshi soam 20MSC010

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INDEX

• Linearly And Circularly Polarized Light

• Circular Birefringence And Circular Dichroism
• ORD And CD Curves
• Cotton Effect
• Empirical Rules- Octant Rule
• Axial α– Haloketone Rule

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PLANE POLARIZED LIGHT

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CIRCULARLY POLARIZED LIGHT

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CIRCULAR BIREFRINGENCE
• Symmetric compounds have same refractive index for the LCPL and
the RCPL. Dissymmetric compounds have different refractive indices
for the two types of circularly polarized light, the LCPL and the RCPL.
This phenomenon is called as the circular birefringence.

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 T = t1

ACHIRAL ENVIRONMENT CHIRAL ENVIRONMENT 10

T= 0

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CIRCULAR DICHROISM

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CIRCULAR DICHROISM
• Circular dichroism is due to different absorption of the right and left
circularly polarized light in a chiral environment.

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CD CURVE
• The measurement of ellipticity as a function of wavelength is known
as CIRCULAR DICHROISM.

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OPTICAL ROTATORY DISPERSION
• The measurement of optical activity as a function of wavelength is
known as optical rotatory dispersion.( BASED ON CIRCULAR
BIREFRINGENCE)

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COTTON EFFECT
The graph shows an anomalous behaviour with a peak and a trough.
This anomalous behaviour is called the Cotton Effect (CE).

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• It is the result of the unequal refractive indices (circular birefringence)
and the unequal absorption for the LCPL and the RCPL (circular
dichroism).
• When the peak appears at a longer λ, compared to the trough, the
ORD curve is called as the positive CE curve and when the peak
appears at a shorter λ, compared to the trough, the ORD curve is
called as the negative CE curve.

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Nature of cotton effect
• structure
• Configuration
• conformation

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OCTANT RULE

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AXIAL α HALOKETONE RULE
• This empirical rule was shown to correlate the sign of the CE of chiral
cyclohexanone derivatives with presence of an axial halogen atom at
the axial-position with respect to the carbonyl group.

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REFERENCES
• Nasipuri, D. STEREOCHEMISTRY OF ORGANIC COMPOUNDS, fourth
edition.; NEW AGE INTERNATIONAL (P) LIMITED , PUBLISHERS.

• KARNIK, A. V.; HASAN, M. Stereochemistry A Three Dimensional

Insight; Elsevier.

• MOHAN, J. ORGANIC SPECTROSCOPY Principles and Applications, 2nd

edition.; alpha science.

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THANK YOU

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