CHEM 430 Lecture 9 - UV Spectroscopy 2014

Spring 2014
UV Spectroscopy
I.
Introduction
A. UV radiation and Electronic Excitations
1. The difference in energy between molecular bonding, nonbonding and anti-bonding orbitals ranges from 125-650 kJ/mole
2.
This energy corresponds to EM radiation in the ultraviolet (UV)

region, 100-350 nm, and visible (VIS) regions 350-700 nm of the
spectrum
3.
For comparison, recall the EM spectrum:
-rays
X-rays
UV
IR
Microwave
Radio
Visible
4.
Using IR we observed vibrational transitions with energies of 840 kJ/mol at wavelengths of 2500-15,000 nm
5.
For purposes of our discussion, we will refer to UV and VIS

spectroscopy as UV
UV Spectroscopy
I.
Introduction
B. The Spectroscopic Process
1. In UV spectroscopy, the sample is irradiated with the broad
spectrum of the UV radiation
2. If a particular electronic transition matches the energy of a
certain band of UV, it will be absorbed
3. The remaining UV light passes through the sample and is
observed
4. From this residual radiation a spectrum is obtained with gaps
at these discrete energies this is called an absorption spectrum
UV Spectroscopy
I.
Introduction
C. Observed electronic transitions
1. The lowest energy transition (and most often obs. by UV) is
typically that of an electron in the Highest Occupied Molecular
Orbital (HOMO) to the Lowest Unoccupied Molecular Orbital
(LUMO)
2.
For any bond (pair of electrons) in a molecule, the molecular

orbitals are a mixture of the two contributing atomic orbitals; for
every bonding orbital created from this mixing (, ), there is a
corresponding anti-bonding orbital of symmetrically higher
energy (*, *)
3.
The lowest energy occupied orbitals are typically the likewise,

the corresponding anti-bonding orbital is of the highest
energy
-orbitals are of somewhat higher energy, and their

complementary anti-bonding orbital somewhat lower in energy
than *.
5.
Unshared pairs lie at the energy of the original atomic orbital,
UV Spectroscopy
I.
Introduction
6. Here is a graphical representation
Unoccupied levels
Energy
Atomic orbital
Atomic orbital
Occupied levels
Molecular orbitals
UV Spectroscopy
I.
Introduction
7. From the molecular orbital diagram, there are several possible
electronic transitions that can occur, each of a different relative
energy:
Energy
alkanes
carbonyls
unsaturated cmpd
O, N, S, halogens
carbonyls
UV Spectroscopy
I.
Introduction
7. Although the UV spectrum extends below 100 nm (high energy),
oxygen in the atmosphere is not transparent below 200 nm
8.
Special equipment to study vacuum or far UV is required
9.
Routine organic UV spectra are typically collected from 200-700

nm
10. This limits the transitions that can be observed:

150 nm
alkanes
carbonyls
170 nm
unsaturated cmpds.180 nm
O, N, S, halogens
190 nm
carbonyls
300 nm
- if conjugated!
UV Spectroscopy
I.
Introduction
D. Selection Rules
1. Not all transitions that are possible are observed
2.
For an electron to transition, certain quantum mechanical

constraints apply these are called selection rules
3.
For example, an electron cannot change its spin quantum

number during a transition these are forbidden
Other examples include:
the number of electrons that can be excited at one
time
symmetry properties of the molecule
symmetry of the electronic states
4.
To further complicate matters, forbidden transitions are

sometimes observed (albeit at low intensity) due to other factors
UV Spectroscopy
I.
Introduction
E. Band Structure
1. Unlike IR (or later NMR), where there may be upwards of 5 or
more resolvable peaks from which to elucidate structural
information, UV tends to give wide, overlapping bands
2.
It would seem that since the electronic energy levels of a pure

sample of molecules would be quantized, fine, discrete bands
would be observed for atomic spectra, this is the case
3.
In molecules, when a bulk sample of molecules is observed, not

all bonds (read pairs of electrons) are in the same vibrational
or rotational energy states
4.
This effect will impact the wavelength at which a transition is

observed very similar to the effect of H-bonding on the O-H
vibrational energy levels in neat samples
UV Spectroscopy
I.
10
Introduction
E. Band Structure
5. When these energy levels are superimposed, the effect can be
readily explained any transition has the possibility of being
observed
Disassociation
R1 - Rn
V4
R1 - Rn
V3
R1 - Rn
V2
V1 R1 - Rn
E1
Vo
R1 - Rn
Disassociation
Energy
R1 - Rn
V4
R1 - Rn
V3
R1 - Rn
E0
V2
V1 R1 - Rn
Vo
R1 - Rn
UV Spectroscopy
II.
11
Instrumentation and Spectra

A. Instrumentation
1. The construction of a traditional UV-VIS spectrometer is very
similar to an IR, as similar functions sample handling,
irradiation, detection and output are required
2.
Here is a simple schematic that covers most modern UV

spectrometers:
I0
I0
detector
monochromator/
beam splitter optics
I0
sample
UV-VIS sources
reference
log(I0/I) = A
200
, nm
700
UV Spectroscopy
II.
12

A. Instrumentation
3. Two sources are required to scan the entire UV-VIS band:
Deuterium lamp covers the UV 200-330
Tungsten lamp covers 330-700
4.
As with the dispersive IR, the lamps illuminate the entire band of
UV or visible light; the monochromator (grating or prism)
gradually changes the small bands of radiation sent to the beam
splitter
5.
The beam splitter sends a separate band to a cell containing the

sample solution and a reference solution
6.
The detector measures the difference between the transmitted

light through the sample (I) vs. the incident light (I0) and sends
this information to the recorder
UV Spectroscopy

A. Instrumentation
7. As with dispersive IR, time is required to cover the entire UV-VIS
band due to the mechanism of changing wavelengths
8.
A recent improvement is the diode-array spectrophotometer here a prism (dispersion device) breaks apart the full spectrum
transmitted through the sample
9.
Each individual band of UV is detected by a individual diodes on

a silicon wafer simultaneously the obvious limitation is the size
of the diode, so some loss of resolution over traditional
instruments is observed
Diode array
UV-VIS sources
sample
II.
13
Polychromator
entrance slit and dispersion device
UV Spectroscopy
II.
14

B. Instrumentation Sample Handling
1. Virtually all UV spectra are recorded solution-phase
2.
Cells can be made of plastic, glass or quartz
3.
Only quartz is transparent in the full 200-700 nm range; plastic

and glass are only suitable for visible spectra
4.
Concentration (we will cover shortly) is empirically determined
A typical sample cell (commonly called a cuvet):
UV Spectroscopy
II.
15

5. 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
6.
Since spectra are only obtained up to 200 nm, solvents typically

only need to lack conjugated systems or carbonyls
Common solvents and cutoffs:
acetonitrile
190
chloroform
240
cyclohexane
195
1,4-dioxane
215
95% ethanol
205
n-hexane
methanol
isooctane
water
190
201
205
195
UV Spectroscopy
II.
16

7. Additionally solvents must preserve the fine structure (where it
is actually observed in UV!) where possible
8.
H-bonding further complicates the effect of vibrational and

rotational energy levels on electronic transitions, dipole-dipole
interacts less so
9.
The more non-polar the solvent, the better (this is not always
possible)
UV Spectroscopy
II.
17

C. The Spectrum
1. The x-axis of the spectrum is in wavelength; 200-350 nm for UV,
200-700 for UV-VIS determinations
2.
Due to the lack of any fine structure, spectra are rarely shown in
their raw form, rather, the peak maxima are simply reported as
a numerical list of lamba max values or max
NH2
max =
O
206 nm
252
317
376
UV Spectroscopy
II.
18

C. The Spectrum
1. The y-axis of the spectrum is in absorbance, A
2.
From the spectrometers point of view, absorbance is the inverse

of transmittance: A = log10 (I0/I)
3.
From an experimental point of view, three other considerations

must be made:
1. a longer path length, l through the sample will cause
more UV light to be absorbed linear effect
2.
3.
the greater the concentration, c of the sample, the

more UV light will be absorbed linear effect
some electronic transitions are more effective at the

absorption of photon than others molar absorptivity,
this may vary by orders of magnitude
UV Spectroscopy
II.
19

C. The Spectrum
4. These effects are combined into the Beer-Lambert Law:
cl
A=
i.
for most UV spectrometers, l would remain constant

(standard cells are typically 1 cm in path length)
ii.
concentration is typically varied depending on the strength

of absorption observed or expected typically dilute sub .
001 M
iii. molar absorptivities vary by orders of magnitude:

i. values of 104-106 are termed high intensity
absorptions
ii. values of 103-104 are termed low intensity absorptions
iii. values of 0 to 103 are the absorptions of forbidden
transitions
A is unitless, so the units for are cm-1 M-1 and are rarely
expressed
UV Spectroscopy
II.
20

D. Practical application of UV spectroscopy
1. UV was the first organic spectral method, however, it is rarely
used as a primary method for structure determination
2.
It is most useful in combination with NMR and IR data to

elucidate unique electronic features that may be ambiguous in
those methods
3.
It can be used to assay (via max and molar absorptivity) the

proper irradiation wavelengths for photochemical experiments,
or the design of UV resistant paints and coatings
4.
The most ubiquitous use of UV is as a detection device for HPLC;

since UV is utilized for solution phase samples vs. a reference
solvent this is easily incorporated into LC design
UV is to HPLC what mass spectrometry (MS) will be to GC
UV Spectroscopy
21
III. Chromophores
A. Definition
1. Remember the electrons present in organic molecules are
involved in covalent bonds or lone pairs of electrons on atoms
such as O or N
2.
Since similar functional groups will have electrons capable of

discrete classes of transitions, the characteristic energy of these
energies is more representative of the functional group than the
electrons themselves
3.
A functional group capable of having characteristic electronic

transitions is called a chromophore (color loving)
4.
Structural or electronic changes in the chromophore can be

quantified and used to predict shifts in the observed electronic
transitions
UV Spectroscopy
22
III. Chromophores
B. Organic Chromophores
1. Alkanes only posses -bonds and no lone pairs of electrons, so
only the high energy * transition is observed in the far UV
This transition is destructive to the molecule, causing cleavage
of the -bond
C
UV Spectroscopy
23
III. Chromophores
Alcohols, ethers, amines and sulfur compounds in the cases of
simple, aliphatic examples of these compounds the n * is the
most often observed transition; like the alkane * it is most
often at shorter than 200 nm
Note how this transition occurs from the HOMO to the LUMO
CN
nN sp
CN
N
anitbonding
orbital
UV Spectroscopy
24
III. Chromophores
3. Alkenes and Alkynes in the case of isolated examples of these
compounds the * is observed at 175 and 170 nm,
respectively
Even though this transition is of lower energy than *, it is
still in the far UV however, the transition energy is sensitive to
substitution
UV Spectroscopy
25
III. Chromophores
4. Carbonyls unsaturated systems incorporating N or O can
undergo
n * transitions (~285 nm) in addition to *
Despite the fact this transition is forbidden by the selection rules
( = 15), it is the most often observed and studied transition for
carbonyls
This transition is also sensitive to substituents on the carbonyl
Similar to alkenes and alkynes, non-substituted carbonyls
undergo the * transition in the vacuum UV (188 nm, =
900); sensitive to substitution effects
UV Spectroscopy
26
III. Chromophores
4. Carbonyls n * transitions (~285 nm); * (188 nm)
CO transitions omitted for clarity
It has been
determined from
spectral studies, that
carbonyl oxygen
more approximates
sp rather than sp2 !
UV Spectroscopy
27
III. Chromophores
C. Substituent Effects
General from our brief study of these general chromophores, only
the weak n * transition occurs in the routinely observed UV
The attachment of substituent groups (other than H) can shift
the energy of the transition
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
UV Spectroscopy
28
III. Chromophores
General Substituents may have any of four effects on a
chromophore
Bathochromic shift (red shift) a shift to longer ; lower
energy
Hypsochromic shift (blue shift) shift to shorter ; higher
energy
Hyperchromic effect an increase in intensity
Hypochromic effect a decrease in intensity
Hypsochromic
Bathochromic
Hypochromic
200 nm
Hyperchromic
700 nm
UV Spectroscopy
29
III. Chromophores
1. Conjugation most efficient means of bringing about a
bathochromic and hyperchromic shift of an unsaturated
chromophore:
nm
H2C
max
CH2
175
15,000
217
21,000
258
35,000
465
125,000
-carotene
O
n * 280
* 189
12
900
n * 280
* 213
27
7,100
UV Spectroscopy
30
III. Chromophores
1. 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, 1 and
2 from two sp2 hybrid carbons combine to form two MOs 1 and
2* in ethylene
UV Spectroscopy
31
III. Chromophores
When we consider butadiene, we are now mixing 4 p orbitals
giving 4 MOs of an energetically symmetrical distribution
compared to ethylene
E for the HOMO LUMO transition is reduced
UV Spectroscopy
32
III. Chromophores
Extending this effect out to longer conjugated systems the
energy gap becomes progressively smaller:
Energy
Lower energy =
Longer wavelenghts
ethylene
butadiene
hexatriene
octatetraene
UV Spectroscopy
33
III. Chromophores
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 -system
A
Energy
nA
UV Spectroscopy
34
III. Chromophores
Methyl groups also cause a bathochromic shift, even though
they are devoid of - or n-electrons
This effect is thought to be through what is termed
hyperconjugation or sigma bond resonance
H
C
C
H
H
UV Spectroscopy
35
Next time We will find that the effect of substituent groups can be reliably quantified
from empirical observation of known conjugated structures and applied to new
systems
This quantification is referred to as the Woodward-Fieser Rules which we will apply
to three specific chromophores:
1. Conjugated dienes
2. Conjugated dienones
3. Aromatic systems
max = 239 nm
UV Spectroscopy
36
IV. Structure Determination

A. Dienes
1. General Features
For acyclic butadiene, two conformers are possible s-cis and strans
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
UV Spectroscopy
37

A. Dienes
1. General Features
Two possible * transitions can occur for butadiene
and 2 4*

s-trans
175 nm forb.
217 nm
175 nm
253 nm
s-cis
The 2 4* transition is not typically observed:

1. The energy of this transition places it outside the
region typically observed 175 nm
2.
For the more favorable s-trans conformation, this

transition is forbidden
The 2 3* transition is observed as an intense absorption
UV Spectroscopy
38

A. Dienes
1. General Features
The 2 3* 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:
max = 217
nm
253
220
227
227
256
263
UV Spectroscopy
39

A. Dienes
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 *
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)
UV Spectroscopy
40

A. Dienes
2. Woodward-Fieser Rules - Dienes
The rules begin with a base value for max 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
Extended conjugation
Increment
+30
Each exo-cyclic C=C
+5
Alkyl
+5
-OCOCH3
+0
-OR
+6
-SR
+30
-Cl, -Br
-NR2
+5
+60
UV Spectroscopy
41

A. Dienes
2. Woodward-Fieser Rules - Dienes
For example:
Isoprene - acyclic butadiene = 217 nm
one alkyl subs.
+5
nm
Experimental value
Allylidenecyclohexane
- acyclic butadiene =
one exocyclic C=C
2 alkyl subs.
Experimental value
222 nm
220 nm
217 nm
+ 5 nm
+10 nm
232 nm
237 nm
UV Spectroscopy
42

A. Dienes
3. Woodward-Fieser Rules Cyclic Dienes
There are two major types of cyclic dienes, with two different
base values
Heteroannular (transoid):
= 5,000 15,000
base max = 214
Homoannular (cisoid):
= 12,000-28,000
base max = 253
The increment
table is the same as Increment
for acyclic butadienes with a
Group
couple additions:
Additional
homoannular
Where both types of

diene are present, the
one with the longer
becomes the base
+39
UV Spectroscopy
43

A. Dienes
In the pre-NMR era of organic spectral determination, the power
of the method for discerning isomers is readily apparent
Consider abietic vs. levopimaric acid:
C OH
O
abietic acid
C OH
O
levopimaric acid
UV Spectroscopy
44

A. Dienes
For example:
1,2,3,7,8,8a-hexahydro-8amethylnaphthalene
diene =
214 nm
heteroannular
3 alkyl subs. (3 x 5)
+15 nm
1 exo C=C
+ 5 nm
234 nm
Experimental value
235 nm
UV Spectroscopy
45

A. Dienes
C OH
O
heteroannular diene =
214 nm
1 exo C=C
+20 nm
+ 5 nm
239 nm
homoannular diene =
253 nm
1 exo C=C
+20 nm
+ 5 nm
C OH
O
278 nm
UV Spectroscopy
46

A. Dienes
Be careful with your assignments three common errors:
R
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
UV Spectroscopy
47

B. Enones
1. General Features
Carbonyls, as we have discussed have two primary electronic
transitions:
Remember, the * transition is

allowed and gives a high e, but lies
outside the routine range of UV
observation
The n * transition is forbidden
and gives a very low e, but can
routinely be observed
UV Spectroscopy
48

B. Enones
1. General Features
For auxochromic substitution on the carbonyl, pronounced
hypsochromic shifts are observed for the n * transition (max):
O
H
293 nm
O
CH3
279
Cl
235
NH2
214
O
O
O
OH
204
204
This is explained by the inductive

withdrawal of electrons by O, N or
halogen from the carbonyl carbon this
causes the n-electrons on the carbonyl
oxygen to be held more firmly
It is important to note this is different
from the auxochromic effect on *
which extends conjugation and causes
a bathochromic shift
In most cases, this bathochromic shift is
not enough to bring the *
transition into the observed range
UV Spectroscopy
49

B. Enones
1. General Features
Conversely, if the C=O system is conjugated both the n *
and * bands are bathochromically shifted
Here, several effects must be noted:
the effect is more pronounced for *
if the conjugated chain is long enough, the much

higher intensity * band will overlap and drown
out the n * band
the shift of the n * transition is not as predictable
For these reasons, empirical Woodward-Fieser rules for

conjugated enones are for the higher intensity, allowed *
transition
UV Spectroscopy
50

B. Enones
1. General Features
These effects are apparent from the MO diagram for a
conjugated enone:
UV Spectroscopy
51

B. Enones
C C C
2. Woodward-Fieser Rules - Enones
O

C C C C C
Group
Increment
6-membered ring or acyclic enone
Base 215
nm
5-membered ring parent enone
Base 202
nm
Acyclic dienone
Base 245
nm
Double bond extending conjugation
30
Alkyl group or ring residue
and higher
10, 12, 18
-OH
and higher
35, 30, 18
-OR
35, 30, 17,

31
-Cl
15, 12
-Br
25, 30
95
-O(C=O)R
-NR2
Exocyclic double bond
UV Spectroscopy
52

B. Enones
Aldehydes, esters and carboxylic acids have different base
values than ketones
Unsaturated system
Base Value
Aldehyde
208
With or alkyl groups
220
230
With alkyl groups
242
Acid or ester
208
217
Group value exocyclic double

bond
+5
Group value endocyclic bond

in 5 or 7 membered ring
+5
UV Spectroscopy
53

B. Enones
Unlike conjugated alkenes, solvent does have an effect on max
These effects are also described by the Woodward-Fieser rules
Solvent correction
Water
Increment
+8
Ethanol, methanol
Chloroform
-1
Dioxane
-5
Ether
-7
Hydrocarbon
-11
UV Spectroscopy
54

B. Enones
Some examples keep in mind these are more complex than
dienes
cyclic enone =
215
O
nm
2 x - alkyl subs. (2 x 12) +24
nm
239 nm
Experimental value
238 nm
cyclic enone =
extended conj.
b-ring residue
d-ring residue
exocyclic double bond
215 nm
+30 nm
+12 nm
+18 nm
+ 5 nm
280 nm
Experimental
280 nm
UV Spectroscopy
55

B. Enones
Take home problem can these two isomers be discerned by UVspec
O
O
Eremophilone
allo-Eremophilone
Problem Set 1: (text) 1,2,3a,b,c,d,e,f,j, 4, 5, 6 (1st, 2nd and 5th

pairs), 8a, b, c
Problem Set 2: outside problems/key -Tuesday
UV Spectroscopy
56

C. Aromatic Compounds
1. General Features
Although aromatic rings are among the most widely studied and
observed chromophores, the absorptions that arise from the
various electronic transitions are complex
On first inspection, benzene has six -MOs, 3 filled , 3 unfilled
*
UV Spectroscopy
57

1. General Features
One would expect there to be four possible HOMO-LUMO *
transitions at observable wavelengths (conjugation)
Due to symmetry concerns and selection rules, the actual
transition energy states of benzene are illustrated at the right:
u
200 nm
(forbidden
)
260 nm
(forbidden
)
u
u
180 nm
(allowed)
UV Spectroscopy
58

1. General Features
The allowed transition ( = 47,000) is not in the routine range of
UV obs. at 180 nm, and is referred to as the primary band
The forbidden transition ( = 7400) is observed if substituent
effects shift it into the obs. region; this is referred to as the
second primary band
At 260 nm is another forbidden
transition ( = 230), referred to
as the secondary band.
This transition is fleetingly allowed
due to the disruption of symmetry
by the vibrational energy states,
the overlap of which is observed
in what is called fine structure
UV Spectroscopy
59

1. General Features
Substitution, auxochromic, conjugation and solvent effects can
cause shifts in wavelength and intensity of aromatic systems
similar to dienes and enones
However, these shifts are difficult to predict the formulation of
empirical rules is for the most part is not efficient (there are
more exceptions than rules)
There are some general qualitative observations that can be
made by classifying substituent groups --
UV Spectroscopy
60

2. Substituent Effects
a. Substituents with Unshared Electrons
IV. If the group attached to the ring bears n electrons,
they can induce a shift in the primary and secondary
absorption bands
V.
Non-bonding electrons extend the -system through

resonance lowering the energy of transition *
VI. More available n-pairs of electrons give greater shifts

G
UV Spectroscopy
61

The presence of n-electrons gives the possibility of n
* transitions
If this occurs, the electron now removed from G,

becomes an extra electron in the anti-bonding *
orbital of the ring
This state is referred to as a charge-transfer excited

state
*
*
UV Spectroscopy
62

pH can change the nature of the substituent group
deprotonation of oxygen gives more available n-pairs,
lowering transition energy
protonation of nitrogen eliminates the n-pair,
raising transition energy
Primary
Secondary
Substitue
nt
max
max
-H
203.5
7,400
254
204
-OH
211
6,200
270
1,450
-O-
235
9,400
287
2,600
-NH2
230
8,600
280
1,430
-NH3+
203
7,500
254
169
-C(O)OH
230
11,600
273
970
-C(O)O-
224
8,700
268
560
UV Spectroscopy
63

b. Substituents Capable of -conjugation
When the substituent is a -chromophore, it can
interact with the benzene -system
With benzoic acids, this causes an appreciable shift in

the primary and secondary bands
For the benzoate ion, the effect of extra n-electrons

from the anion reduces the effect slightly
Primary
Secondary
Substitue
nt
max
max
-C(O)OH
230
11,600
273
970
-C(O)O-
224
8,700
268
560
UV Spectroscopy
64

c. Electron-donating and electron-withdrawing effects
No matter what electronic influence a group exerts,
the presence shifts the primary absorption band to
longer
Electron-withdrawing groups exert no influence on the

position of the secondary absorption band
Electron-donating groups increase the and of the

secondary absorption band
UV Spectroscopy
65

c. Electron-donating and electron-withdrawing effects
Electron withdrawing
Electron donating
Primary
Secondary
Substituent
max
max
-H
203.5
7,400
254
204
-CH3
207
7,000
261
225
-Cl
210
7,400
264
190
-Br
210
7,900
261
192
-OH
211
6,200
270
1,450
-OCH3
217
6,400
269
1,480
-NH2
230
8,600
280
1,430
-CN
224
13,000
271
1,000
C(O)OH
230
11,600
273
970
-C(O)H
250
11,400
-C(O)CH3
224
9,800
-NO2
269
7,800
UV Spectroscopy
66

d. Di-substituted and multiple group effects
With di-substituted aromatics, it is necessary to
consider both groups
If both groups are electron donating or withdrawing,

the effect is similar to the effect of the stronger of the
two groups as if it were a mono-substituted ring
If one group is electron withdrawing and one group

electron donating and they are para- to one another,
the magnitude of the shift is greater than the sum of
both the group effects
Consider p-nitroaniline:
O
H2N
O
H2N
N
O
UV Spectroscopy
67

If the two electonically dissimilar groups are ortho- or
meta- to one another, the effect is usually the sum of
the two individual effects (meta- no resonance; orthosteric hind.)
For the case of substituted benzoyl derivatives, an

empirical correlation of structure with observed max
has been developed
This is slightly less accurate than the Woodward-Fieser

rules, but can usually predict within an error of 5 nm
O
R
UV Spectroscopy
68

Parent Chromophore
max
R = alkyl or ring
residue
246
R=H
250
R = OH or O-Alkyl
230
Substituent increment
Alkyl or ring residue
10
-O-Alkyl, -OH, -O-Ring
25
-O-
11
20
78
-Cl
10
-Br
15
-NH2
13
13
58
-NHC(O)CH3
20
20
45
-NHCH3
-N(CH3)2
73
20
20
85
UV Spectroscopy
69

d. Polynuclear aromatics
When the number of fused aromatic rings increases,
the for the primary and secondary bands also
increase
For heteroaromatic systems spectra become complex

with the addition of the n * transition and ring size
effects and are unique to each case
UV Spectroscopy
V.
70
Visible Spectroscopy
A. Color
1. General
The portion of the EM spectrum from 400-800 is observable
to humans- we (and some other mammals) have the
adaptation of seeing color at the expense of greater detail
400
500
600
, nm
Violet
400-420
Indigo
420-440
Blue
440-490
Green
490-570
Yellow
570-585
Orange
585-620
Red
620-780
700
800
UV Spectroscopy
V.
71
A. Color
1. General
When white (continuum of ) light passes through, or is
reflected by a surface, those ls that are absorbed are
removed from the transmitted or reflected light
respectively
What is seen is the complimentary colors (those that are

not absorbed)
This is the origin of the color wheel
UV Spectroscopy
V.
72
A. Color
1. General
Organic compounds that are colored are typically those
with extensively conjugated systems (typically more than
five)
Consider -carotene
-carotene, max = 455 nm
max is at 455 in the far blue region of

the spectrum this is absorbed
The remaining light has the
complementary color of orange
UV Spectroscopy
V.
73
A. Color
1. General
Likewise:
lycopene, max = 474 nm

O
H
N
N
H
O
indigo
max for lycopene is at 474 in the near blue region

of the spectrum this is absorbed, the compliment
is now red
max for indigo is at 602 in the orange region of the
spectrum this is absorbed, the compliment is now
indigo!
UV Spectroscopy
V.
74
A. Color
1. General
One of the most common class of colored organic
molecules are the azo dyes:
N N
EWGs
EDGs
From our discussion of di-subsituted aromatic

chromophores, the effect of opposite groups is greater
than the sum of the individual effects more so on this
heavily conjugated system
Coincidentally, it is necessary for these to be opposite for
the original synthetic preparation!
UV Spectroscopy
V.
75
A. Color
1. General
These materials are some of the more familiar colors of our
environment
NO2
HO
H2N
N
N
OH
N N
O3S
N N
NH2
SO3
Para Red
Fast Brown
Sunset Yellow (Food Yellow 3)
76
The colors of M&Ms

Bright Blue
Royal Blue
Common Food Uses

Beverages, dairy products, powders, jellies,
confections, condiments, icing.
Common Food Uses

Baked goods, cereals, snack foods, ice-cream,
confections, cherries.
Orange-red
Lemon-yellow
Common Food Uses

Gelatins, puddings, dairy products, confections,
beverages, condiments.
Common Food Uses

Custards, beverages, ice-cream, confections,
preserves, cereals.
Orange
Common Food Uses
Cereals, baked goods, snack foods, ice-cream,
beverages, dessert powders, confections
UV Spectroscopy
V.
77
A. Color
1. General
In the biological sciences these compounds are used as
dyes to selectively stain different tissues or cell structures
Biebrich Scarlet - Used with picric acid/aniline blue for

staining collagen, recticulum, muscle, and plasma. Luna's
method for erythrocytes & eosinophil granules. Guard's
method for sex chromatin and nuclear chromatin.
HO
O3S
N N
N N
SO3
UV Spectroscopy
V.
78
A. Color
1. General
In the chemical sciences these are the acid-base indicators
used for the various pH ranges:
Remember the effects of pH on aromatic substituents
Methyl Orange
O3S
N N
Yellow, pH > 4.4
CH3
N
CH3
O3S
H
N N
Red, pH < 3.2
CH3
N
CH3

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CHEM 430 Lecture 9 - UV Spectroscopy 2014

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Spring 2014

This energy corresponds to EM radiation in the ultraviolet (UV)

For comparison, recall the EM spectrum:

For purposes of our discussion, we will refer to UV and VIS

For any bond (pair of electrons) in a molecule, the molecular

The lowest energy occupied orbitals are typically the likewise,

-orbitals are of somewhat higher energy, and their

Unshared pairs lie at the energy of the original atomic orbital,

Special equipment to study vacuum or far UV is required

Routine organic UV spectra are typically collected from 200-700

10. This limits the transitions that can be observed:

For an electron to transition, certain quantum mechanical

For example, an electron cannot change its spin quantum

To further complicate matters, forbidden transitions are

It would seem that since the electronic energy levels of a pure

In molecules, when a bulk sample of molecules is observed, not

This effect will impact the wavelength at which a transition is

Instrumentation and Spectra

Here is a simple schematic that covers most modern UV

Instrumentation and Spectra

The beam splitter sends a separate band to a cell containing the

The detector measures the difference between the transmitted

Instrumentation and Spectra

Each individual band of UV is detected by a individual diodes on

Instrumentation and Spectra

Cells can be made of plastic, glass or quartz

Only quartz is transparent in the full 200-700 nm range; plastic

Concentration (we will cover shortly) is empirically determined

A typical sample cell (commonly called a cuvet):

Instrumentation and Spectra

Since spectra are only obtained up to 200 nm, solvents typically

Instrumentation and Spectra

H-bonding further complicates the effect of vibrational and

Instrumentation and Spectra

Instrumentation and Spectra

From the spectrometers point of view, absorbance is the inverse

From an experimental point of view, three other considerations

the greater the concentration, c of the sample, the

some electronic transitions are more effective at the

this may vary by orders of magnitude

Instrumentation and Spectra

for most UV spectrometers, l would remain constant

concentration is typically varied depending on the strength

iii. molar absorptivities vary by orders of magnitude:

Instrumentation and Spectra

It is most useful in combination with NMR and IR data to

It can be used to assay (via max and molar absorptivity) the

The most ubiquitous use of UV is as a detection device for HPLC;

Since similar functional groups will have electrons capable of

A functional group capable of having characteristic electronic

Structural or electronic changes in the chromophore can be

CO transitions omitted for clarity

Hyperchromic effect an increase in intensity

Hypochromic effect a decrease in intensity

E for the HOMO LUMO transition is reduced

IV. Structure Determination

The s-cis conformer is at an overall higher potential energy than

IV. Structure Determination

The 2 4* transition is not typically observed: