BS Hons.

Chemistry (6th Semester)

Topic:-
Factors influencing the λmax value

Submitted to: Submitted by:

Miss Shazia Samra Ashiq (330)
Asma Saeed (336)
 Contents

 Chromophore
 Auxoxhrome
 Conjugated system
 Conjugated diene system
 Woodward – Fieser’s rules for
conjugated dienes, trienes, polyenes
 Woodward-Fieser Rules for
Calculating the λmax of Conjugated
Carbonyl Compounds
 Aromatic system
 Spectroscopy
“Spectroscopy is the branch of the science deals with the study of interaction of Electro Magnetic
Radiation (EMR) with matter”

Absorption Spectroscopy: the type and amount of the radiation, which is absorbed depend
upon the structure of the molecules and the numbers of molecules interacting with the radiation. The
study of these dependencies is called absorption spectroscopy. (UV, IR, NMR, X-Ray

Factors influencing the λmax value:

 Chromophore
 Auxoxhrome
 Conjugated system
 Conjugated diene system
 Aromatic system
Chromophore
An atom or group whose presence is responsible for the colour of a compound.The structural feature in
a molecule , such as the carbonyl group in aldehyde and ketones, that is responsible for the absorption
of electromagnetic radiation in the UV/VIS region, is called chromophore.

The chromophore generally contain some degree of unsaturation. The wavelength of maximum
absorption for a compound depends not only on the nature of the chromophore present in the molecule
but also on the environment of the chromophore.

Types
 Dependent chromophore
 Independent chromophore
Independent chromophore
When a single chromophore is sufficient to impart colour to the compound called independent
chromophore.

Example
Azo group (-N=N-)

Nitro group (-NO)

Dependent chromophore
When more than one chromophore is required to produce colour in the compound called dependent
chromophores.

Example
Carbonyl compounds, alkenes

Auxochrome
The substituents which themselves do not show absorption i.e whish are not chromophores, but when
attached to a chromophore they cause an increase in the intensity of the absorption, and possibly the
wavelength , are called as Auxochrome.

Example
The methoxy group in methyl vinyl ether

CH2=CHOCH3 shift the π- π* absorption of the ethylenic double bond from 171 nm to 190 nm.

Effect of conjugation
All auxochromic group contain non bonding electrons which are in chromophore. It is this conjugation
which shifts the λmax to a longer wavelength.

Types
 Bathochromic effect or red shift
 Hypsochromic effect or blue shift
 Hyperchromic effect
 Hypochromic effect
Bathochromic effect or red shift
The shift of the λmax to a longer wavelength.

Hypsochromic effect or blue shift

A shift to a shorter wavelength.
Hyperchromic effect
An increase in the intensity of absorption caused by a substituent.

Hypochromic effect
Decrease in the intensity of absorption.

Conjugated systems
The conjugation of an auxochrome with a chromophore shifts the π- π* absorption to a longer
wavelength. The most dramatic effect is observed when a chromophore is in conjugation with another
chromophore as, e.g. in 1,3-butadiene or in α,β-unsaturated carbonyl compounds. In fact the
importance of UV/VIS spectroscopy lies in its ability to determine the presence,nature, and extent of
conjugation.

Example 1
1,3-butadiene absorbs at 217 nm ,whereas ethylene absorbs at 171 nm. In 1,3-butadiene, the π orbital
of the two ethylenic bonds combine to form four new π molecular orbitals, two bonding(π 1 and π2) and
two anti bonding (π*3 and π*4)
 Energy gap between the highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO) in butadiene is smaller than in ethylene(ethene)
Addition of successive conjugated double bonds progressively narrows the gap between
HOMO and LUMO
Thus longer wavelength (lower energy) radiation required for the transition
Example 2
In case of 1,3,5-hexatriene,the difference in energy between the highest occupied molecular orbital and
the lowest unoccupied molecular orbital is further reduced and absorption occur at a still longer
wavelength 1,3,5-hexatriene absorbs at 258 nm.
Thus progressively increasing conjugation moves the absorption maxima to longer wavelength and
finally into visible region.

The compounds having a conjugated system of nine double bonds are usually yellow in color. The red
colour of tomatoes and carrots arise from conjugated molecules of this type.
 molecule wavelength of maximum absorption (nm)

ethene 171

buta-1,3-diene 217

hexa-1,3,5-triene 258

The same principle applies when unlike chromophores are in conjugation with each other as, e.g, in α,β-
unsaturated carbonyl compounds. Methyl vinyl ketone, CH2=CHCOCH3, shows π- π* absorption at 215
nm, while neither the carbonyl group nor the isolated double bond shows π- π* absorption above 200
nm.

Conjugated diene system

The effect of substituents on the wavelength of absorption especially in dienes, is additive so that the
position of absorption is influenced in a systematic way. Certain empirical rules were formulated by
Woodward, and later amplified by Fieser, to predict the position of absorption in open chain dienes and
dienes in sex membered rings.( the rule show much better agreement of dienes in rings).

The successful application of these rules lies in choosing the correct base value of the diene,and then
adding the contribution made by each additional feature. It is therefore important to recognized the
diene system correctly.

Types
There are two distinct diene system

 Heteroannular diene
 Homoannular diene
Homo-annular conjugated double bonds Are the conjugated double bond present in
the same ring. it is also called as Homodiene. some examples of this type are:
Hetero-annular conjugated double bonds Are the double bonds which are present in
different ring.

for example.

Endocyclic double bond

The double bond present in a ring only (inside).

Exocyclic double bond

The double bond is a part of the ring (outside).

Woodward – Fieser’s rules for conjugated dienes,

trienes, polyenes
According to this rules each type of dienes or triens system is having a certain fixed value at which
absorption takes place.

This constitutes the basic value or parent value.

This value of absorption maximum depends upon ……

(I) The number of alkyl substitution or ring residues

(II) The number of double bonds which extending conjugation

(III) The presence s of polar groups such as Cl, Br, OR, are added to the basic value to obtain λ max for a
particular compound.

The parent values and increment for different substituents / groups

(A) Parent value :-

1) Homo annular conjugated diene λ 253 nm

2) Hetero annular conjugated diene Acyclic conjugated diene λ 214 nm

3)Acyclic conjugated diene λ 214 nm

4) Butadiene system open chain (Acyclic) λ 217 nm

5) Acyclic triens λ 245 nm

(B) Increment :-

1) Each alkyl substitution or ring residue λ + 5 nm

2) Exocyclic double bond λ +5 nm

3) Double bond extending conjugation λ +30 nm

(C) Auxochromes :-

-O- alkyl λ +6 nm

-S-alkyl λ +30 nm

-Cl, -Br λ +5 nm

-N(alkyl)2 λ +60 nm

-OCOCH3 λ 0 nm
EXAMPLES

1. Calculate absorption maximum in UV Spectrum of 2,4 Hexadiene.

CH3
H3C

Butadiene system; basic value = 217nm

2 Alkyl substituent(2X5nm) = 10nm

Calculated value = 227 nm

Observed value = 227 nm

2. Calculate λ max for 1,4- dimethylcyclohex-1,3-diene

Parent value for homoannular ring : = 253 nm

Two alkyl substituents : 2 x 5 = 10 nm
Two ring residue : 2 x 5 = 10 nm

calculated value : = 273 nm

observed value : = 263 nm

3. Calculate λ max of following compound

Parent value for heteroannular diene : = 214 nm

Four ring residue : 4 X5 = 20 nm

Calculated value : = 234 nm

Observed value : = 236 nm
Parent value for heteroannular diene : = 214 nm
3 ring residue : 3 X5 = 15 nm
Exocyclic double bond = 5 nm
Thiomethyl substituent =30 nm

Calculated value : = 264 nm

Observed value : = 268 nm

Acyclic butadiene = 217 nm

Extended conjugation = +30 nm

Calculated value = 247 nm

Acyclic base = 217 nm
2 alkyl substitution = 10 nm

Calculated value = 227 nm

Parent value for heteroannular : = 214 nm

Four ring residue : 4 X5 = 20 nm
Exocyclic double bond =5 nm

Calculated value : = 239 nm

Observed value : = 236 nm

Parent value for homoannular : = 253 nm

Extended conjugation 1 X30 = 30 nm
Alkyl substitution 2x5 =10 nm

Calculated value : = 293 nm

Parent value for homoannular (the highest value) : = 253 nm
Extended conjugation 1 X30 = 30 nm
Exocyclic double bond =5 nm
Alkyl substitution or ring residue 6x5 =30 nm

Calculated value : = 318 nm

Woodward-Fieser Rules for Calculating the λmax of

Conjugated Carbonyl Compounds
Woodward-Fieser rules can be extended to calculate the λmax of α,β-unsaturated carbonyl
compounds. In a similar manner to Woodward rules for dienes discussed previously, there is
base value to which the substituent effects can be added and the λmax can be calculated using the
formula:
λmax = Base value + Σ Substituent Contributions + Σ Other Contributions

Core Chromophores With Base Values

As Woodward and Fieser have listed, α,β-unsaturated carbonyl compounds have a range of
influence on the λmax of the molecule depending upon:

1] The type of carbonyl functionality present. For example, α,β-unsaturated aldehyde

contribute 210 nm while α,β-unsaturated ketones contribute 215 nm and α,β-unsaturated
esters contribute 195 nm.
2] If the core is a part of a cyclic ring. For example, cyclopentenone contribution is 202
nm whilecyclohexenone is 215 nm.

3] If the conjugation is extended to γ,δ-positions to form dienes. For example, in such cases, a
simple addition of 30 nm to the base value of the α,β-unsaturated carbonyl compound gives
appropriate estimates to the observed influences.

Note- In cases of α,β-γ,δ-diene carbonyl compounds like those shown above, the extended
conjugation at the α,β-γ,δ-positions is accounted for in the base value of the core chromophore
and need not be added separately. If however there is another substituent at the α,β-γ,δ-
positions, then you must add an additional + 30 nm for each. Also the bond shown as β-γ is not
counted as β substituent but as a part of the core chromophore and need not be added
separately.
Substituent Effects
According to Woodward, in case of α,β-unsaturated carbonyl compounds, the location of the
substituent is significant in determining the influence on the wavelength of maximum
absorption. Substituents can be located on either α, β positions. If the conjugation is extended
to γ and δ positions, then substitutions at these position also play a vital role in determining the
practical λmax.

1] Substituents at α-Position
As we can see the from table 3 below the effect of different substituent when placed on the α-
position.

Effect of substituents on the α-position of α,β-unsaturated carbonyl compounds

Substituent Influence

-R (Alkyl group) + 10 nm

-OR (Alkoxy group) + 35 nm

-Cl (Chloro group) + 15 nm

-Br (Bromo group) + 25 nm

-OH (alcohol/hydroxyl) + 35 nm

-OC(O)R (Acyloxy/Ester) + 6 nm
2] Substituents at β-Position
As we can see the from table 4 below the effect of different substituent when placed on the β-
position.

Effect of substituents on the β-position of α,β-unsaturated carbonyl compounds

Substituent Influence

-R (Alkyl group) + 12 nm

-OR (Alkoxy group) + 30 nm

-Cl (Chloro group) + 12 nm

-Br (Bromo group) + 30 nm

 -OH (alcohol/hydroxyl) + 30 nm

-OC(O)R (Acyloxy/Ester) + 6 nm

-SR (Sulfide) + 85 nm

-NR2 (Amine) + 95 nm
3] Substituents at γ and δ-position
As we can see the from table 5 below the effect of different substituent when placed on the γ or
δ position.

Effect of substituents on the γ or δ position of α,β-γ,δ-diene carbonyl compound.

Substituent Influence

-R (Alkyl group) (both γ and δ) + 18 nm

-OC(O)R (Acyloxy/Ester)
(both γ and δ) + 6 nm

-Cl (Chloro) (both γ and δ) + 12 nm

-Br (Bromo) (both γ and δ) + 30 nm

-OH (alcohol/hydroxyl group)

(only γ) + 50 nm

-OR (Alkoxy group) (only γ) + 30 nm

Other Contributors
1] Exocyclic Double Bonds
In general exocyclic double bonds add an additional + 5 nm to the base value. In order to
identify exocyclic double bonds we recommend you read the previous chapter on how to use
Woodward-Fieser rules to calculate the λmax of conjugated dienes and polyenes. We
have explained it extensively there.
2] Solvent Effects
Since carbonyl functional groups have polarity, solvents play an important role in how the
electronics of the structure play out. The rules are simple and straight forward:

Solvent Influence
 Water – 8 nm

Methanol/Ethanol – 1 nm

Ether + 6 nm

Hexane / Cyclohexane + 7 nm
3] Homoannular Cyclohexadiene
In a special case where you have α,β-γ,δ-diene carbonyl compound and both the double bonds
are present within one ring system you get a homoannular or homocyclic cyclohexadiene
carbonyl compound. In such a case you must add an additional 35 nm to the system.

Aromatic system
Benzene display three absorption bands, all originating from π- π* transitions. It absorbs at 184 nm
(Ɛ, 60,000) and at 204 nm (Ɛ, 7,400) and has a fine structure (multiple peaks) in the region between
230 and 270 nm with λmax at 254 nm of relatively low intensity (Ɛ, 200) resulting from forbidden
transition, due to the loss of symmetry caused by molecular vibrations. The first two bands
(ethylenic) of benzene are generally designated as E1 and E2 bands, while the fine structure
(benzenoid) is designated as B band. The fine structure is characteristic of almost all the simple
aromatic compounds.
In fact, most aromatic compounds consist of three absorption bands, all due to π- π* transitions.
However the position of those bands may be modified (generally move to higher wavelength) in
substituted benzene and other aromatic compounds.

Unfortunately, prediction of the effects of various substituents is not always possible in the manner
similar to that in the case of dienes and α,β-unsaturated carbonyl compounds; only some of the
observed trends can be described.

Substituents of simple alkyl groups on the benzene ring produces a small bathochromic effect with
a slight increase in intensity, but does not destroy the structure. the red shift is attributed to
hyperconjugation in which methyl group is more effective than other alkyl groups.

Substituents of auxochromic groups (OH,NH2, etc) causes a pronounced red shift with large
intensification, and loss of the fine structure, because of the conjugation between non bonding and
the π electrons. Generally, the more extensive the conjugation, the less obvious is the vibrational
fine structure. Altering the availability of the non bonding electron will alter the wavelength of
maximum absorption.

For example conversion of phenol to its anion results in a pronounced red shift and an increased
intensity. Similarly with aniline is converted to the anilinium cation, it results in a blue shift and a
spectrum almost identical to that of benzene is obtained , except that the fine structure is absent,
attachment of an unsaturated group such as ethylenic, acetylenic, nitrile,aldehydic, carboxylic and
nitro, to the benzene ring produces a red shift often a great degree.

The condensed rings aromatic hydrocarbons retain the absorption pattern, including the fine
structure, typical of benzene. However, as the number of condensed rings increases, the absorption
is shifted progressively to longer wavelength, until it appears in the visible region. E2 bands of
naphthacene (λmax 480nm ;Ɛ, 11,000)and pentacene (λmax 580 nm; Ɛ, 12,600) occur in the visible
region.
Reference
1. Woodward, R. B. Structure and Absoprtion Spectra. IV. Further Observations on α,β-
Unsaturated Ketones. J. Am. Chem. Soc. 1942. 64(1), 76-77.

2. Woodward, R. B. Clifford, A. F. Structure and Absoprtion Spectra. II. 3-Acetoxy-Δ5-(6)-nor-

cholestene-7-carboxylic Acid. J. Am. Chem. Soc. 1941. 63(10), 2727-2729.

3. Spectroscopic Determination of Organic Compounds, 5th Edition, Silverstein, Bassler,

Morrill 1991.

4. Kalsi, P. S. Spectroscopy of Organic Compounds. 6th Edition, New Age International

Publishers, New Delhi, 2004.

5. Glagovich, N. Woodward’s rules for conjugated carbonyl compounds.

[Online]http://www.chemistry.ccsu.edu/glagovich/teaching/316/uvvis/conjugated.html (
Accessed on July 27, 2012).

6. Author Unknown. Michigan State University – Department of Chemistry. Woodward-Fieser

Rules for Calculating the π to π* λmax of Conjugated Carbonyl Compounds.
[Online]http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/UV-
Vis/uvspec.htm (Accessed on July 27, 2012).