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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
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
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
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
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
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
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
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
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)
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
Y4 *
175 nm –forb. 175 nm
Y3 *
217 nm 253 nm
Y2
s-trans s-cis
Y1
Consider:
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:
1 exo C=C + 5 nm
234 nm
* *
Ring Ring
residue + residue +
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
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
Aldehyde 208
Acid or ester