UV-Vis Spectroscopy

CHM622-ADVANCE ORGANIC SPECTROSCOPY

 Nature of electronic transitions
Absorption spectrum

Energy absorption
-atoms/ molecule pass from ground state to
exited state

HOMO
-highest occupied molecular orbital

LUMO
-lowest occupied molecular orbital
 Nature of electronic transitions
 What happens when light is absorbed by
molecules? In each possible case, an electron is excited
from a full orbital into an empty anti-bonding
 Promotion of electrons
orbital. Each jump takes energy from the light,
 When light passes through the compound, energy and a big jump obviously needs more energy
from the light is used to promote an electron from than a small one.
a bonding or non-bonding orbital into one of the
empty anti-bonding orbitals.
 Nature of electronic transitions
 Each wavelength of light What is the relationship between the energy gap and the
has a particular energy wavelength absorbed ?
associated with it. Relationship between the frequency of light absorbed and its
energy:
 If that particular amount
of energy is just right for
making one of these
energy jumps, then that
wavelength will be
absorbed - its energy will
have been used in
promoting an electron
From the above equation:
For high energy jump (greater energy gap) , you will have to
absorb light of a higher frequency. The greater the frequency,
the greater the energy.
 Nature of electronic transitions
 Because UV-visible absorption spectra are always given using wavelengths of light
rather than frequency, thus the relationship between wavelength and frequency is
given as:
 Second equation which relate with wavelength:

Important summary
The larger the energy
jump, the lower the
wavelength of the light
absorbed.

 You can see from this that the higher the frequency is, the lower the wavelength is.
 So . . . If you have a bigger energy gap, you will absorb light with a higher
frequency - which is the same as saying that you will absorb light with a lower
wavelength.
 Nature of electronic transitions
 An absorption spectrometer works in a range from about 200 nm (in the near ultra-violet) to
about 800 nm (in the very near infra-red). Only a limited number of the possible electron jumps
absorb light in that region
 The important jumps are shown in black, and a less important one in grey. The grey dotted
arrows show jumps which absorb light outside the region of the spectrum we are working in.
 Remember that bigger jumps/gaps need more energy and so absorb light with a shorter
wavelength. The jumps shown with grey dotted arrows absorb UV light of wavelength less that
200 nm
 Instrumentation
A DOUBLE BEAM UV-VISIBLE ABSORPTION
SPECTROMETER

Different substances absorb different wavelengths of light

help to identify - the presence of particular metal ions or
of particular functional groups in organic compounds

The amount of absorption is dependent on the

concentration of the substance if it is in solution
Instrumentation
A DOUBLE BEAM UV-VISIBLE ABSORPTION
SPECTROMETER
 Instrumentation
The light source The diffraction grating and the slit
 You need a light source which gives  You are probably familiar with the way
the entire visible spectrum plus the that a prism splits light into its component
near ultra-violet so that you are colours. A diffraction grating does the
covering the range from about 200 nm same job, but more efficiently.
to about 800 nm. (This extends slightly  The blue arrows show the way the various
into the near infra-red as well.)
wavelengths of the light are sent off in
 You can't get this range of different directions. The slit only allows
wavelengths from a single lamp, and light of a very narrow range of
so a combination of two is used - a wavelengths through into the rest of the
deuterium lamp for the UV part of the spectrometer.
spectrum, and a tungsten / halogen  By gradually rotating the diffraction
lamp for the visible part.
grating, you can allow light from the
 The combined output of these two whole spectrum (a tiny part of the range
bulbs is focussed on to a diffraction at a time) through into the rest of the
grating. instrument.
 Instrumentation
The rotating discs
 Each disc is made up of a number of different segments. Those in the machine we are
describing have three different sections.

 The light coming from the diffraction grating and slit will hit the rotating disc and one
of three things can happen.
 If it hits the transparent section, it will go straight through and pass through the cell
containing the sample. It is then bounced by a mirror onto a second rotating disc.
 This disc is rotating such that when the light arrives from the first disc, it meets the
mirrored section of the second disc. That bounces it onto the detector.
 It is following the red path in the diagram:

 If the original beam of light from the slit hits the mirrored
section of the first rotating disc, it is bounced down along
the green path. After the mirror, it passes through a
reference cell.
 Finally the light gets to the second disc which is rotating in
such a way that it meets the transparent section. It goes
straight through to the detector.
 instrumentation

The sample and reference cells

 These are small rectangular glass or quartz containers. They are often designed so
that the light beam travels a distance of 1 cm through the contents.
 The sample cell contains a solution of the substance you are testing - usually very
dilute. The solvent is chosen so that it doesn't absorb any significant amount of
light in the wavelength range we are interested in (200 - 800 nm).
 The reference cell just contains the pure solvent
 Instrumentation
 If I is less than Io, the sample has absorbed some of
The detector and computer the light. convert into absorbance of the sample -
 The detector converts the given the symbol, A.
incoming light into a current.  The relationship between A and the two intensities is
The higher the current, the given by:
greater the intensity of the light.
 For each wavelength of light
passing through the
spectrometer, the intensity of  the absorbance ranges from 0 to 1.
the light passing through the  An absorbance of 0 at some wavelength means that
reference cell is measured. This no light of that particular wavelength has been
is usually referred to as Io - absorbed.
that's I for Intensity.  The intensities of the sample and reference beam are
both the same, so the ratio Io/I is 1. Log10 of 1 is zero.
 The intensity of the light passing
 An absorbance of 1 happens when 90% of the light at
through the sample cell is also
measured for that wavelength - that wavelength has been absorbed - which means
given the symbol, I. that the intensity is 10% of what it would otherwise
be.
 In that case, Io/I is 100/I0 (=10) and log10 of 10 is 1.
 Principles of absorption spectroscopy

Beer-Lambert Law
 Instrumentation
The chart recorder
 Chart recorders usually plot absorbance against wavelength. The output
might look like this:

 This particular substance has what are known as absorbance peaks at 255
and 395 nm.
 Solvent
 The non-conjugated solvents are most
suitable for this purpose.
 Should not absorb UV radiation in the same
region as in the substance/sample whose
spectrum is being determined.
 Show fine structure of an absorption band.
Non-polar solvent did not form hydrogen
bond with solute. Spectrum of solute
closely to spectrum gases state – fine
structure observed
 Polar solvent- hydrogen bond solute-
solvent complex. Fine structure disappear

UV spectra of phenol in ethanol

and isooctane, respectively
 Solvent
 Solvents must be transparent in the
region to be observed; the wavelength
where a solvent is no longer
transparent is referred to as the cutoff.
 Since spectra are only obtained up to
200 nm, solvents typically only need to
lack conjugated p systems or
carbonyls.
 Common solvents and cutoffs points
or minimum region of transparency:
 acetonitrile 190
 1,4-dioxane 215
 n-hexane 201
 water 190
 What is Chromophore?
Chromophore:
 Groups/functional group in a molecule which absorb light
Organic Chromophores
Alkanes – only posses s-bonds and no lone pairs of
electrons, so only the high energy s  s* transition is
observed in the far UV since they absorb UV light at a very
short wavelength.
This transition is destructive to the molecule, causing
cleavage of the s-bond
s*
C C

s C C
Alkenes and Alkynes
– in the case of isolated examples of these compounds
the p  p* is observed at 175 and 170 nm, respectively.
Even though this transition is of lower energy than s
 s*, it is still in the far UV – however, the transition
energy is sensitive to substitution

p*

p
Alcohols, ethers, amines and sulfur compounds
– in the cases of simple, aliphatic examples of these
compounds the n  s* is the most often observed
transition; like the alkane s  s* it is most often at
shorter l than 200 nm

Note how this transition occurs from the HOMO to the

LUMO for amine (RNH2)

C N
s*CN

C N

nN sp
3
C N anitbonding
orbital

sCN C N
 Carbonyls – n  p* transitions (~285 nm); p  p* (188 nm)

p*

n C O

p
O

sCO transitions omitted for clarity

 Substituents that increase the intensity and often
wavelength of an absorption are called auxochromes.

 Common auxochromes include alkyl, hydroxyl, alkoxy

and amino groups and the halogens.
 General – Substituents may have any of four effects
on a chromophore
 Bathochromic shift (red shift) – a shift to longer l;
lower energy
 Hypsochromic shift (blue shift) – shift to shorter l;

Hyperchromic
higher energy
 Hyperchromic effect – an increase in intensity
e
 Hypochromic effect – a decrease in intensity Hypsochromic Bathochromic

Hypochromic
200 nm 700 nm
 The effect of conjugation
lmax nm e

Conjugation: H2C 175 15,000

CH2
Effect of Bathochromic shift
-due to increase the extent 217 21,000
of conjugation in double-
bond system
-electronic energy levels of 258 35,000
chromophore move close
together
-need less energy to excite
from HOMO to LUMO 465 125,000
-thus, the wavelength of
light absorbed become -carotene
longer
O
n  p* 280 12
p  p* 189 900

O n  p* 280 27
p  p* 213 7,100
Substituent Effects
Conjugation – Alkenes
 The observed shifts from conjugation imply that an
increase in conjugation decreases the energy required for
electronic excitation

 From molecular orbital (MO) theory two atomic p

orbitals, f1 and f2 from two sp2 hybrid carbons combine to
form two MOs Y1 and Y2* in ethylene
Y 2*

f1 f2

Y1 p
Conjugation – Alkenes
 When we consider butadiene, we are now mixing 4 p orbitals
giving 4 MOs of an energetically symmetrical distribution
compared to ethylene

Y 4*
Y 2*

Y 3*

Y2

Y1 p
Y1

DE for the HOMO  LUMO transition is reduced

 Conjugation – Alkenes
 Extending this effect out to longer conjugated systems the
energy gap becomes progressively smaller:


Energy Lower energy =

Longer wavelengths

ethylene
butadiene
hexatriene
octatetraene
Conjugation – Alkenes
Similarly, the lone pairs of electrons on N, O, S, X can
extend conjugated systems – auxochromes
Here we create 3 MOs – this interaction is not as
strong as that of a conjugated p-system

Y3*

p* Y2

nA

Y1
Conjugation – Alkenes
Methyl groups also cause a bathochromic shift, even
though they are devoid of p- or n-electrons
This effect is thought to be through what is termed
“hyperconjugation” or sigma bond resonance
 result from overlap of C-H bonding with the Π system

C
H
C C H
 Woodward-Fieser Rules
which we will apply to three specific chromophores:
1.Conjugated dienes
2.Conjugated dienones
3.Aromatic systems

2.Woodward-Fieser Rules
Woodward and the Fiesers performed extensive studies of terpene and
steroidal alkenes and noted similar substituents and structural features would
predictably lead to an empirical prediction of the wavelength for the lowest
energy p  p* electronic transition

This work was distilled by Scott in 1964 into an extensive treatise on the
Woodward-Fieser rules in combination with comprehensive tables and examples –
(A.I. Scott, Interpretation of the Ultraviolet Spectra of Natural Products, Pergamon,
NY, 1964)

A more modern interpretation was compiled by Rao in 1975 – (C.N.R. Rao,

Ultraviolet and Visible Spectroscopy, 3rd Ed., Butterworths, London, 1975)

Woodward and Fieser – enables to predict the wavelength at which diene will absorb.
Structure Determination
A. Dienes
General Features
For acyclic butadiene, two conformers are possible –
s-cis and s-trans

s-trans s-cis

The s-cis conformer is at an overall higher potential

energy than the s-trans; therefore the HOMO
electrons of the conjugated system have less of a
jump to the LUMO – lower energy, longer wavelength
 Two possible p  p* transitions can occur for
butadiene Y2  Y3* and Y2  Y4*

Y4*
175 nm –forb. 175 nm
Y3*
217 nm 253 nm
Y2
s-trans s-cis
Y1

The Y2  Y4* transition is not typically observed:

 The energy of this transition places it outside the region typically
observed – 175 nm

 For the more favorable s-trans conformation, this transition is forbidden

The Y2  Y3* transition is observed as an intense
absorption
 The Y2  Y3* transition is observed as an intense
absorption (e = 20,000+) based at 217 nm within the
observed region of the UV

While this band is insensitive to solvent (as would be

expected) it is subject to the bathochromic and
hyperchromic effects of alkyl substituents as well as
further conjugation

Consider:

lmax = 217 253 220 227 227 256 263 nm

Woodward-Fieser Rules - Dienes
The rules begin with a base value for lmax of the
chromophore being observed:

acyclic butadiene = 217 nm

The incremental contribution of substituents is added

to this base value from the group tables:
Group Increment
Extended +30
conjugation
Each exo-cyclic C=C +5
Alkyl, ring residue +5
-OCOCH3 +0
-OR +6
-SR +30
-Cl, -Br +5
-NR2 +60
Woodward-Fieser Rules - Dienes
For example:

Isoprene - acyclic butadiene = 217 nm

one alkyl subs. + 5 nm
222 nm
Experimental value 220 nm

Allylidenecyclohexane
acyclic butadiene = 217 nm
one exocyclic C=C + 5 nm
2 alkyl subs (2x5) +10 nm
232 nm
Experimental value 237 nm
 3.Woodward-Fieser Rules –
Cyclic Dienes
There are two major types of
cyclic dienes, with two Group Increment
different base values Extended +30
conjugation
Each exo-cyclic +5
C=C
Alkyl, ring +5
residue
Homoannular (Cisoid) Heteroannular (transoid) -OCOCH3 +0
e = 12,000-28,000 e = 5,000 – 15,000 -OR +6
base lmax = 253 base lmax = 214
-SR +30
-Cl, -Br +5
The increment table is the -NR2 +60
same as for acyclic
butadienes with a couple
additions:
3.Woodward-Fieser Rules – Cyclic Dienes
For example:

heteroannular diene = 214 nm

3 ring residue (3 x 5) +15 nm

1 exo C=C + 5 nm
234 nm

Experimental value 235 nm

  Woodward-Fieser Rules – Cyclic Dienes

* *

Ring Ring
residue + residue +

Note: exocyclic double bond* will be found at a conjugation points on ring

 Notice that:

This compound has three exocyclic

double bonds; the indicated bond is
exocyclic to two rings

This is not a heteroannular diene; you would

use the base value for an acyclic diene

Likewise, this is not a homooannular diene;

you would use the base value for an acyclic
diene
Structure Determination
Enones
1.General Features
Carbonyls, as we have discussed have two primary
electronic transitions:

p* Remember, the p  p* transition is

allowed and gives a high e, but lies
outside the routine range of UV
observation
n
The n  p* transition is forbidden and
gives a very low e, but can routinely be
observed
General Features
For auxochromic substitution on the carbonyl,
pronounced hypsochromic shifts are observed for the
n  p* transition (lmax):

O
This is explained by the inductive withdrawal
H 293
of electrons by O, N or halogen from the
O carbonyl carbon – this causes the n-electrons
CH3 on the carbonyl oxygen to be held more
279 firmly
O

Cl 235 It is important to note this is different from

the auxochromic effect on p  p* which
O
extends conjugation and causes a
NH2
214 bathochromic shift
O
In most cases, this bathochromic shift is not
O 204 enough to bring the p  p* transition into
O
the observed range
OH 204
General Features
Conversely, if the C=O system is conjugated both the
n  p* and p  p* bands are bathochromically shifted

Here, several effects must be noted:

i. the effect is more pronounced for p  p*

ii.if the conjugated chain is long enough, the

much higher intensity p  p* band will overlap
and drown out the n  p* band

iii.the shift of the n  p* transition is not as

predictable

For these reasons, empirical Woodward-Fieser rules

for conjugated enones are for the higher intensity,
allowed p  p* transition
General Features
These effects are apparent from the MO diagram for
a conjugated enone:

Y4 *

p* p*
Y3 *

n n

Y2

p p
Y1
O O
  a d g  a
 Woodward-Fieser Rules - Enones  C C C d C C C C C
O O
Group Increment
6-membered ring or Base 215 nm
acyclic enone
5-membered ring parent Base 202 nm
enone
Acyclic dienone Base 245 nm
increment
Double bond extending 30
conjugation
Alkyl group or ring a, , g and higher 10, 12, 18
residue
-OH a, , d 35, 30, 50
-OR a, , g, d 35, 30, 17, 31
-O(C=O)R a, , d 6
-Cl a,  15, 12
-Br a,  25, 30
-NR2  95
Exocyclic double bond 5
Homocyclic diene 39
component
Examples
Woodward-Fieser Rules - Enones
Aldehydes, esters and carboxylic acids have different
base values than ketones
Unsaturated system Base Value

Aldehyde 208

With a or  alkyl groups 220

With a, or , alkyl groups 230

With a,, alkyl groups 242

Acid or ester

With a or  alkyl groups 208

With a, or , alkyl groups 217

Group value – exocyclic a, +5

double bond
Group value – endocyclic a, +5
bond in 5 or 7 membered ring
 Aromatic compounds
 Has 2 types of peaks primary & secondary peaks
 Substitution on benzene ring will effect bathochromic and hyperchromic
shift
 Substituents with unshared electrons
 Substituents capable of Π conjugation
 Electron-releasing and withdrawing effect
 Disubstituted benzene derivatives
 Polynuclear aromatic hydrocarbon & heterocyclic compound