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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 the  You are probably familiar with the way that
entire visible spectrum plus the near a prism splits light into its component
ultra-violet so that you are covering the colours. A diffraction grating does the same
range from about 200 nm to about 800 job, but more efficiently.
nm. (This extends slightly into the near
 The blue arrows show the way the various
infra-red as well.)
wavelengths of the light are sent off in
 You can't get this range of wavelengths different directions. The slit only allows light
from a single lamp, and so a of a very narrow range of wavelengths
combination of two is used - a through into the rest of the spectrometer.
deuterium lamp for the UV part of the
 By gradually rotating the diffraction grating,
spectrum, and a tungsten / halogen
you can allow light from the whole
lamp for the visible part.
spectrum (a tiny part of the range at a
 The combined output of these two bulbs time) through into the rest of the instrument.
is focussed on to a diffraction grating.
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
The detector and computer light. convert into absorbance of the sample - given
 The detector converts the the symbol, A.
incoming light into a current. The  The relationship between A and the two intensities is
higher the current, the greater given by:
the intensity of the light.
 For each wavelength of light
passing through the  the absorbance ranges from 0 to 1.
spectrometer, the intensity of  An absorbance of 0 at some wavelength means that
the light passing through the no light of that particular wavelength has been
reference cell is measured. This is absorbed.
usually referred to as Io - that's I  The intensities of the sample and reference beam are
for Intensity. 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 that wavelength has been absorbed - which means
measured for that wavelength - that the intensity is 10% of what it would otherwise be.
given the symbol, I.  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 sp3 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; higher

Hyperchromic
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 different Group Increment
base values Extended +30
conjugation
Each exo-cyclic +5
C=C
Alkyl, ring residue +5
-OCOCH3 +0
Homoannular (Cisoid) Heteroannular (transoid) -OR +6
e = 12,000-28,000 e = 5,000 – 15,000
base lmax = 253 -SR +30
base lmax = 214
-Cl, -Br +5
-NR2 +60
The increment table is the 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
on the carbonyl oxygen to be held more
279
CH3
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
     
 Woodward-Fieser Rules - Enones  C C C  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 residue , ,  and higher 10, 12, 18
-OH , ,  35, 30, 50
-OR , , ,  35, 30, 17, 31
-O(C=O)R , ,  6
-Cl ,  15, 12
-Br ,  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  or  alkyl groups 220

With , or , alkyl groups 230

With ,, alkyl groups 242

Acid or ester

With  or  alkyl groups 208

With , or , alkyl groups 217

Group value – exocyclic , +5


double bond
Group value – endocyclic , +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

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