Chapter 01: UV-Vis Spectroscopy

(Calculating lambda max of organic compounds)

L1_P1: A chromophore is a group which when attached to a saturated hydrocarbon provides a
molecule that absorbs a maximum of visible or UV radiation at some specific wavelength. There can
be more than one wavelength as well where absorption takes place.

Auxochromes are groups which when introduced into an absorbing system causes a bathochromic
shift which is the shift of the lambda max to a longer wavelength.

Consider benzene. Benzene is a chromophore. It absorbs at 3 wavelengths: 180 nm, 204 nm and 255
nm. The longest wavelength it absorbs at is 255 nm. The structure of benzoic acid consists of a
benzene ring in which a hydrogen atom on one carbon has been substituted with a carboxylic acid
group. The carboxylic acid group is an auxochrome. It shifts the longest wavelength at which
absorption takes place in benzene from 255 nm to 273 nm.

Conjugated double bonds are double bonds separated by a single bond. Double bonds themselves
are chromophores. When double bonds are present in a compound as conjugated double bonds, the
length of the chromophore is extended. The electronic energy levels of the chromophore move
closer together. The energy required to produce an electronic transition from the highest occupied
molecular orbital to the lowest unoccupied molecular orbital decreases. Therefore, the wavelength
at which radiation is absorbed shifts to a longer wavelength. Ethene has a single double bond.
Butadiene has two double bonds which are conjugated. Hexatriene has three double bonds which
are conjugated. As the number of conjugated double bonds increase, so does the wavelength at
which absorption takes place from 175 nm in ethene to 258 nm in hexatriene. Beta-carotene which
has 11 double bonds in conjugation absorbs at 465 nm.

Similarly, some auxochromes cause bathochromic shifts by extending the length of the chromophore
conjugated system. Benzene has three double bonds in conjugation. Benzaldehyde consists of a
benzene ring where one proton on a carbon atom has been substituted by an aldehyde carbonyl
functional group. The double bond in the carbonyl functional group extends the conjugation in the
benzene ring. Thus, the lowest wavelength at which absorption takes place shifts from 255 nm to
277.5 nm.

A similar effect takes place when an auxochrome has lone pairs of electrons. When the lone pair is
separated by a single bond from the conjugated system, it participates in the conjugated system by
resonance. As a result, the length of the chromophore is extended. The oxygen atom in the hydroxyl
group in phenyl has two lone pairs of electrons. The chlorine atom in the chlorobenzene has three
lone pairs of electrons. The nitrogen atom in the amine group in the aniline has one lone pair of
electrons. These lone pairs all extend conjugation and cause bathochromic shifts in the longest
wavelength at which absorption takes place in benzene.

Methyl groups also produce small bathochromic shifts. This is because of the tendency of methyl
groups to stabilize adjacent unsaturated bonds by hyperconjugation. Hyperconjugation takes place
by the overlap of the carbon hydrogen sigma bond in the methyl group with the pi antibonding
orbital in the adjacent double bond. Toluene consists of a benzene ring with a methyl group. This
extends the longest absorbing wavelength of benzene from 255 nm to 260 nm.

The lambda max of some organic compounds can be predicted. Woodward and Fieser established
some empirical rules for predicting lambda max for dienes and carbonyl compounds. The basic
formula of the rule can be summarized as lambda max equals base value plus substituent
contribution plus other substituent contribution.

L1_P2: The woodward-fieser rule can be applied to calculate the lambda max for dienes and
polyenes.

The first step in predicting lambda max is to identify the core chromophore and select base value.
There are two types of base chromophores. The hetero annular diene or transoid is where the
double bonds are in different planes about the single bond. The base value for this chromophore is
215 nm. The homoanular diene or cisoid is where the double bond is in the same plane about the
single bond. The base value for this chromophore is 253 nm.

The second step is to count the number of alkyl substituent or ring residue. Consider the molecule
given as example. The double bonds are not in the same plane. So, the base value to be selected is
215 nm for the transoid. There are three methyl groups attached to the diene. Each alkyl group or
ring residue increase lambda max by 5 nm. Since there are three alkyl groups, there will be an
increment of total 15 nm. Therefore, the lambda max is the sum of 215 and 15 equaling to 230 nm.

The next step is to identify exocyclic double bonds. Exocyclic double bonds are double bonds that lie
outside a given ring. In example 1 if the B ring is considered, then the double bond in the A ring is an
exocyclic double bond. In example 2, the B ring seems to contain both double bonds. However, both
the double bonds are at junction points on the ring. This means that the double bond may lie in the
A ring as well due to resonance. In example 3 the double bond is outside the two rings.

Consider this example. The double bonds are not in the same plane. So, the base value to be
selected is 215 nm for transoid. There are 3 ring residues attached to the diene. Each alkyl group or
ring residue increases lambda max by 5 nm. There will be an increment of total 15 nm. One of the
double bonds in the diene is exocyclic to the other double bond. Each exercyclic double bond
increase lambda max by 5 nm. Therefore, lambda max is the sum of 215, 15 and 5 equaling to 235
nm.

Consider this molecule. The double bonds are in the same plane. So, the base value to be selected is
253 nm for cisoid. Each alkyl group or ring residue increase lambda max by 5 nm. One alkyl group is
attached to the diene. There are also 3 ring residues attached to the diene giving an increment of 15
nm. One of the double bonds is at a junction between the 2 cycles and so an exercyclic double bond.
Each exercyclic double bond increase lambda max by 5 nm. Therefore, lambda max is the sum of
253, 5, 15 and 5 equaling to 278 nm.

The last step is to identify substituents other than alkyl groups or ring residues. Each substitutent has
different effects on the lambda max as summarized in this table. Consider this molecule. The double
bonds are not in the same plane. So, the base value to be selected is 215 nanometers for transoid.
There are 3 ring residues attached to the diene. Each alkyl group or ring residue increase lambda
max by 5 nm. There will be an increment of total 15 nm. One of the double bonds in the diene is
exercyclic to the other double bond. Each exercyclic double bond increase lambda max by 5 nm.
There is also an alkoxy group attached to the diene. Alkoxy groups increase lambda max by 6 nm.
Therefore, the lambda max is the sum of 215, 15, 5 and 6 equals to 242 nm.
L2_P1: The table shows the lambda max corresponding to alkenes with 3, 4 and 5 conjugated
double bonds. When the number of double bonds in conjugation increase from 3 to 4, lambda max
increases by 45 nm. Again, when the number of double bonds in conjugation increase from 4 to 5,
lambda max increases by 32 nm. The lambda max increase in both cases but it does not increase
proportionally. It became apparent that the woodward-fieser rules could not be applied to
accurately predict lambda max of compounds with more than 4 double bonds.

To overcome this limitation, another empirical rule was developed called the fieser kuhn rules. The
fieser kuhn rules can be used to calculate lambda max of compounds with more than four double
bonds in conjugation. The rule can be summarized as lambda max equals to 114 plus 5 M (where M
is the number of alkyl substituents or ring residues in the conjugated system) plus n (48 - 1.7n)
(where n is the number of conjugated double bonds) minus 16.5Rendo (where R endo is the number
of rings with endocyclic double bonds in the conjugated system) minus 10Rexo (where are Rexo is
the number of rings with exocyclic double bonds in the conjugated system).

An example of the application of this rule is shown with lycophene. Lycopene has 11 double bonds.
So, n equals to 11. There are 8 alkyl substituents. So, M equals to 8. There are no rings. So, both the
value of Rexo and Rendo are 0. Putting these values in the equation for fieser kuhn rule give a
calculated lambda max at 476 nm.

L2_P2: The formula used for calculating lambda max of conjugated carbonyl compounds is the
same as for conjugated dienes. It can be summarized as lambda max equals to base value plus alkyl
substituent contribution plus other substituent contribution.

The first step is to identify the core chromophore and assign a base value. There are four types of
core chromophore.

The first one is the acyclic alpha beta unsaturated carbonyl compound. Here the carbonyl functional
group chromophore is extended to a single carbon-carbon double bond. The base value will depend
on R If R is a hydrogen atom, that is the compound is an alpha beta unsaturated aldehyde, the base
value is 210 nm. If R is an alkyl group, that is the compound is an alpha beta unsaturated ketone, the
base value is 215 nm. If R is an alkoxy group, that is the compound is an alpha beta unsaturated
ester, the base value is 195 nm.

The second type of core chromophore is the acyclic alpha beta gamma delta unsaturated carbonyl
compound. Here the carbonyl functional group chromophore is extended over two conjugated
double bonds. The base value will depend on R. If R is a hydrogen atom, that is the compound is an
alpha beta gamma delta unsaturated aldehyde, the base value is 240 nm. If R is an alkyl group, that
is the compound is an alpha beta gamma delta unsaturated ketone, the base value is 245 nm. If R is
an alkoxy group, that is the compound is an alpha beta gamma delta unsaturated ester, the base
value is 195 nm. Note that these values are equal to the corresponding values for the alpha beta
carbonyl unsaturated compounds after an increment of 30 nm for the double bond extending the
conjugation.

The third type of core chromophore is cyclopentenone. Here the carbonyl functional group
chromophore is part of a five-membered unsaturated ring where the carbon-carbon double bond is
in conjugation with the carbonyl functional group. In this case the base value is 202 nm.
The fourth type of core chromophore is cyclohexenone. Here the carbonyl functional group
chromophore is part of a six-membered unsaturated ring where the carbon-carbon double bond is in
conjugation with the carbonyl functional group. In this case the base value is 215 nm.

The second step is to count the number of alkyl substituents or ring residues. It is important to note
that the position of the substituent has an effect on the value of lambda max. The position is
assigned to the carbon atom in relation to the carbonyl carbonyl functional group. If the carbon
atom is attached to the carbonyl functional group, it is assigned the alpha position. The carbon atom
attached to the alpha carbon is assigned the beta position. The carbon atom attached to the beta
carbon is assigned the gamma position. The carbon atom attached to the gamma carbon is assigned
the delta position. If there is an alkyl group attached to the alpha carbon, there is an increment of 10
nm. If there is an alkyl group attached to the beta carbon then the lambda max is increased by 12
nm. If there is an alkyl group attached to the gamma or delta carbon then lambda max increases by
18 nm.

Consider this molecule. There is one carbon-carbon double bond adjacent to the carbonyl functional
group and it is not in a ring. So, it is an acyclic alpha beta unsaturated carbonyl compound. The R in
the carbonyl functional group is an alkyl group. Therefore, it is an acyclic alpha beta unsaturated
ketone and the base value is therefore selected to be 215 nm. There is one methyl group attached to
the alpha carbon. So, there is an increment of 10 nm. There are two methyl groups attached to the
beta carbon. So, there is an increment of 24 nm. Therefore, the lambda max is the sum of 215, 10
and 24 equaling to 249 nm.

The third step is to identify any exocyclic double bonds. Consider the following molecule. The
carbonyl group is part of a five-membered ring. Therefore, it is a cyclopentenone and the base value
is 202 nm. There are two ring residues attached to the beta carbon. So, there is an increment of 24
nm. The carbon oxygen double bond in the carbonyl group is outside the ring. So, there is an
increment of 5 nm for this exocyclic double bond. Therefore, the lambda max is sum of 202, 24 and 5
equaling to 231 nm.

The fourth step is to identify the other substituents at their correct position. Double bonds extending
conjugation, phenyl groups, exocyclic double bonds and homoannular cyclohexadienes have the
same influence of lambda max regardless of position.

Consider this molecule. The carbonyl functional group is part of a five-membered ring. Therefore, it
is a cyclopentenone and the base value is 202 nm. There are two ring residues attached to the beta
carbon. So, there is an increment of 24 nm. The carbon oxygen double bond is outside the ring. So,
there is an increment of 5 nm for the exocyclic double bond. There is a bromine atom attached to
the alpha carbon. This gives an increment of 25 nm. Therefore, the lambda max is the sum of 202,
24, 5 and 25 equaling to 256 nm.

Now consider this molecule. The carbonyl functional group is part of a six-membered ring.
Therefore, it is a cyclohexenone and the base value is 215 nm. There is one ring residue attached to
the beta carbon. So, there is an increment of 12 nm. There is one ring residue attached to the delta
carbon. So, there is an increment of 18 nm. The carbon oxygen double bond is outside the ring. So,
there is an increment of 5 nm for the exocyclic double bond. There is a double bond extending the
conjugation which gives an increment of 30 nm. Therefore, the lambda max is the sum of 215, 12,
18, 5 and 30 equaling to 280 nm.
L3: Just like the conjugated dienes and conjugated carbonyl compounds, the lambda max for
benzoyl derivative compounds can be predicted using empirical rules. The rule is only applicable for
benzoyl derivatives. These are aromatic compounds containing the carbonyl functional group.

The first step is to identify the core chromophore and select a base value. If the R on the carbonyl
functional group is a hydrogen atom, the base value is 250 nm. If the R on the carbonyl functional
group is an alkyl group or a ring residue, the base value is 246 nm. If the R on the carbonyl functional
group is a hydroxyl or an alkoxy group, the base value is 230 nm.

The second step is to identify the other substituents in their correct position. The position is assigned
to the carbon atom in relation to the carbonyl functional group. If the carbon atom is adjacent to the
carbonyl functional group in the ring, it is assigned the ortho position. If the carbon atom is
separated by one carbon atom from the carbonyl functional group in the ring, it is assigned the meta
position. If the carbon atom is separated by two carbon atoms from the carbonyl functional group in
the ring, it is assigned the para position. The effect of each substituent is different and depends on
its position in the benzene ring.

Consider this example. The R in the carbonyl functional group is an alkyl group. So, the base value is
246 nm. A hydroxyl group is attached to the benzene ring in para position to the carbonyl functional
group. This gives an increment of 25 nm. Therefore, the lambda max is the sum of 246 and 25
equaling to 271 nm.

Now consider the second example. The R in the carbonyl functional group is an alkyl group. So the
base value is 246 nm. A ring residue is attached to the benzene ring in ortho position to the carbonyl
functional group. This gives an increment of 3 nm. An alkoxy group is attached to the benzene ring in
para position to the carbonyl functional group. This gives an increment of 25 nm. Therefore, the
lambda max is the sum of 246, 3 and 25 equaling to 274 nm.

L4: If a UV spectrum of an unknown compound has a single band or peak at a wavelength less than
220 nm and the peak is of low to medium intensity, then it is likely that the band is a result of an n to
sigma star electronic transition. This transition is possible when there is a lone pair of electrons
which is not included in a conjugated system. The unknown compound is likely to have an isolated
amine or alcohol or thiol or ether functional group.

If the UV spectrum of an unknown compound has a single band at wavelength between 250 and 360
nm and the peak is of low intensity, then it is likely that the band is a result of an n to pi star
electronic transition. This transition is possible when there is a simple unconjugated chromophore
that contains an oxygen, nitrogen or sulfur atom. The unknown compound is likely to have an
aldehyde, ketone, amine, nitro, ester, carboxylic acid or amide functional group.

If the UV spectrum of an unknown compound has two bands at wavelength above 200 nm both
having medium intensity with fine structures at the second band, the compound is likely to be a
simple aromatic compound. If the intensity of the second band is high, at longer wavelength and the
fine structures are lost, then the aromatic compound is likely to have substitutions on the ring.

If the UV spectrum of an unknown compound has one band with high intensity at wavelength above
210 nm, the compound is likely to be an alpha beta unsaturated ketone, diene or polyene. The band
results from pi-to-pi star transition. If the band is at longer wavelength, then it may indicate that the
conjugation is extended.
If the UV spectrum of an unknown compound has two bands where one band has low intensity and
is at wavelength above 300 nm and the other band has high intensity and is at wavelength under
250 nm. The compound is likely to be a simple ketone, acid, ester, amide and other compounds
containing both a pi system and lone pairs of electrons. The low intensity band results from an n to
pi star transition and the high intensity band results from a pi-to-pi star transition. If the pi system is
conjugated then the high intensity band may shift to a longer wavelength and hide the low intensity
band.

Compounds that are highly colored absorb in the visible region of the electromagnetic spectrum,
that is the region greater than approximately 400 nm. These compounds are likely to have long-
chain conjugated system or polycyclic aromatic chromophores. beta-carotene is the pigment
responsible for the orange color in carrots. It has 11 double bonds in conjugation and has lambda
max in the visible region of the electromagnetic spectrum.

The UV spectrum of a compound can be used for structural elucidation when NMR an IR spectral
data is unavailable. Unfortunately, it does not provide complete information about the structure of
the compound. If some information about the compound structure is available from IR and NMR
spectroscopy, then the empirical rules can be applied to confirm the structure of an unknown
compound.