CHE 351

Organic Spectroscopy and Aromatic Chemistry

UNIT 1
Introduction to spectroscopy and UV/VIS

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 Wave properties

• EM radiation is conveniently modeled as waves consisting of

perpendicularly oscillating electric and magnetic fields, as
shown below.
y

x
z Electric Field

Magnetic Field

Direction of
propagation
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 Wave parameters
+ Wavelength ()

Electric Field
Amplitude (A)

- Time or Distance

We Use Symbols to Designate the Various Properties of

Waves
  is the wavelength of the waves
 is the frequency of the waves
 c is the speed of light 8

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 Definitions:

 Period (p) – the time required for one cycle to pass a fixed point in
space.

 Frequency() – the number of cycles which pass a fixed point in

space per second.

 Amplitude (A) – The maximum length of the electric vector in the

wave (Maximum height of a wave).

 Wavelength () – The distance between two identical adjacent points

in a wave (usually maxima or minima).

 Wavenumber () - The number of waves per cm in units of cm-1.

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 UV-VIS Spectroscopy
• Ultravialet and visible spectroscopy deals with the recording of the absorption of
radiations in the ultraviolet and visible regions of the electromagnetic spectrum.
• The ultaviolet region extends from 10 to 400 nm. It is subdivided into the near
ultraviolet (quartz) region (200-400 nm) and the far or vacuum ultraviolet region
(10-200 nm).
• The visible region extends from 400 to 800 nm.
• Organic chemists use ultraviolet and visible spectroscopy mainly for detecting the
presence and elucidating the nature of the conjugated multiple bonds or aromatic
rings.

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 Purpose of each Electromagnetic Radiation

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 What we measure
• The desired parameter in spectroscopy is absorbance, but it cannot be directly
measured. Thus, a UV-visible spectrophotometer compares the intensity of the
transmitted radiation with that of the incident UV-visible radiation.

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 UV Spectroscopy

The Spectroscopic Process

 In UV spectroscopy, the sample is irradiated with the broad spectrum
of the UV radiation
 If a particular electronic transition matches the energy of a certain
band of UV, it will be absorbed
 The remaining UV light passes through the sample and is observed
 From this residual radiation a spectrum is obtained with “gaps” at
these discrete energies – this is called an absorption spectrum






11

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 UV Spectroscopy
Observed electronic transitions
 Here is a graphical representation


Unoccupied
LUMO Molecular orbitals


Atomic orbital Non bonding

Energy n orbital

Occupied
HOMO  Molecular orbitals


Molecular orbitals
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 UV Spectroscopy
Observed electronic transitions
 From the molecular orbital diagram, there are several possible
electronic transitions that can occur, each of a different relative
energy:

HUMO    alkanes   carbonyls

LUMO 

Energy   unsaturated cmpds. n  carbonyls

n
Non bonding
orbital

HOMO

LOMO n  O, N, S, halogens

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 UV Spectroscopy

Observed electronic transitions

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 UV Spectroscopy
Observed electronic transitions
 Although the UV spectrum extends below 100 nm (high energy),
oxygen in the atmosphere is not transparent below 200 nm

 Special equipment to study vacuum or far UV is required

 Routine organic UV spectra are typically collected from 200-700

nm

 This limits the transitions that can be observed:

  alkanes 150 nm

  carbonyls 170 nm

  unsaturated cmpds. 180 nm √ - if conjugated!

n  O, N, S, halogens 190 nm

n  carbonyls 300 nm √ 14

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 UV Spectroscopy
Allowed and forbidden transitions
 Transitions between the same symmetry, allowed
 Transitions between different symmetry, forbidden

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 UV Spectroscopy
Allowed and forbidden transitions
  allowed
 X forbidden

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 UV Spectroscopy
Observed electronic transitions
 Although the UV spectrum extends below 100 nm (high energy),
oxygen in the atmosphere is not transparent below 200 nm

 Special equipment to study vacuum or far UV is required

 Routine organic UV spectra are typically collected from 200-700

nm

 This limits the transitions that can be observed:

  alkanes 150 nm

  carbonyls 170 nm

  unsaturated cmpds. 180 nm √ - if conjugated!

n  O, N, S, halogens 190 nm

n  carbonyls 300 nm √ 14

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 UV Spectroscopy
Observed electronic transitions

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 UV Spectroscopy
Observed electronic transitions

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 Experimentally

Violet0 400 - 420 nm Yellow 570 - 585 nm

Indigo 420 - 440 nm Orange 585 - 620 nm
Blue 440 - 490 nm Red 620 - 780 nm
Green 490 - 570 nm

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Tembo ZN (MSc Chemistry, Bed. Sc) CHE 321
 UV Spectroscopy

From an experimental point of view, three other

considerations must be made:
 a longer path length, l, through the
sample will cause more UV light to be
absorbed – linear effect

 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… 19

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 UV Spectroscopy
The Beer-Lambert Law: A= c l

 for most UV spectrometers, l would remain constant (standard

cells are typically 1 cm in path length)

 Concentration c is typically varied depending on the strength of

absorption observed or expected – typically dilute – sub .001 M

 molar absorptivities ε vary by orders of magnitude:

• values of 104-106 are termed high intensity absorptions
• values of 103-104 are termed low intensity absorptions
• values of 0 to 103 are the absorptions of forbidden
transitions

A is unitless, so the units for  are cm-1 x M-1 and are rarely
expressed
Since path length and concentration effects can be easily factored out,
absorbance simply becomes proportional to , and the y-axis is
expressed as  directly or as the logarithm of  20

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 UV Spectroscopy

Selection Rules
 Not all transitions that are possible are observed

 For an electron to transition, certain quantum mechanical

constraints apply – these are called “selection rules”

 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

 To further complicate matters, “forbidden” transitions are

sometimes observed (albeit at low intensity) due to other
factors 21

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 UV Spectroscopy
Instrumentation and Spectra

 Here is a simple schematic that covers most modern UV

spectrometers:

log(I0/I) = A
UV-VIS sources I0 I

sample
200 700

detector
, nm

monochromator/
reference

beam splitter optics I0 I0

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 UV Spectroscopy

Instrumentation and Spectra,

 Two sources are required to scan the entire UV-VIS band:

• Deuterium lamp – covers the UV – 200-330
• Tungsten lamp – covers 330-700

 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

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

the sample solution and a reference solution

 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
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 UV Spectroscopy
Instrumentation – Sample Handling

 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  systems or carbonyls

Common solvents and cutoffs:

acetonitrile 190
chloroform 240
cyclohexane 195
1,4-dioxane 215
95% ethanol 205
n-hexane 201
methanol 205
isooctane 195
water 190

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 MOLECULAR ABSORPTION SPECTRA

 The sharpness of molecular absorption

spectra also depends on the state of the
sample.

 Figure (a) shows an absorption band due

to transitions between electronic-
vibrational-rotational states

 Figure (c) shows a continuous spectra

due to the sample is in the condensed
state. In condensed states the spectra
broaden due to molecular collisions.

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 UV Spectroscopy

 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

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 UV Spectroscopy
Instrumentation – Sample Handling

 Additionally solvents must preserve the fine structure (where it is

actually observed in UV!) where possible

 H-bonding further complicates the effect of vibrational and rotational

energy levels on electronic transitions, dipole-dipole interacts less so

 The more non-polar the solvent, the better (this is not always
possible)

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 STRUCTURE ELUCIDATION

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 WHAT IS A CHROMOPHORE?
• Although the absorption of ultraviolet radiation results from the excitation of
electrons from ground to excited states, the nuclei that the electrons hold
together in bonds play an important role in determining which wavelengths
of radiation are absorbed
• The nuclei determine the strength with which the electrons are bound and
thus influence the energy spacing between ground and excited states
• Hence, the characteristic energy of a transition and the wavelength of
radiation absorbed are properties of a group of atoms rather than of
electrons themselves
• The group of atoms producing such an absorption is called a
chromophore.

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 Saturated molecules
• Alkanes.
• For molecules, such as alkanes, that contain nothing but single bonds
and lack atoms with unshared electron pairs (or pi electrons),
• The only electronic transitions possible are of the  type.
• These transitions are of such a high energy that they absorb ultraviolet
energy at very short wavelengths—shorter than the wavelengths that
are experimentally accessible using typical spectrophotometers.

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 Saturated molecules
• Alcohols, Ethers, Amines, and Sulfur Compounds.
• In saturated molecules that contain atoms bearing nonbonding pairs of
electrons, transitions of the n type become important.

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 Saturated molecules
• Even though the alcohols, ethers, amines, and sulfur
compounds are saturated and they have high-energy
transitions, they do absorb radiation that lies within an
experimentally accessible range.
• Alcohols and amines absorb in the range from 175 to 200 nm,
while organic thiols and sulfides absorb between 200 and 220
nm. Most of the absorptions are below the cutoff points for the
common solvents, so they are not observed in solution spectra.

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 Absorptions of simple isolated chromophore
• You may notice that these simple chromophores nearly all
absorb at approximately the same wavelength (160 to 210 nm)

Basic chromophore
structures

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 Absorptions of simple isolated chromophore
• You may notice that these simple chromophores nearly all
absorb at approximately the same wavelength (160 to 210 nm)

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 Auxochromes
• The attachment of substituent groups in place of hydrogen on a
basic chromophore structure changes the position and intensity
of an absorption band of the chromophore.
• The substituent groups may not give rise to the absorption of
the ultraviolet radiation themselves, but their presence
modifies the absorption of the principal chromophore.
• Substituents that increase the intensity of the absorption, and
possibly the wavelength, are called auxochromes. Typical
auxochromes include methyl, hydroxyl, alkoxy, halogen, and
amino groups

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 Auxochromes
 It has at least one non bonding electron pair that can extend
conjugation with chromophore e.g OH, NH2, COOH, OR

 Note that axochromes do not absorb radiation in UV vis

themselves

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 Wavelength Predictions

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 Wavelength Predictions

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 Wavelength Predictions

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 Wavelength Predictions

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 Wavelength Predictions

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 Wavelength Shifts
• Terminologies of absorption shifts

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 Wavelength Shifts
Hyperhromatic shifts; Increase in
absorption intensity; caused by
axochromatc

Hypsochromatic Bathochromatic(red
(blue) shift; Move to
shift;) Move to longer
shorter wavelength
wavelength cuase by
cause by removal of
axochrome or change
conjugation or change

of solvent of solvent

Hypohromatic decrease in
absorption intensity; Cause by
molecules that change the geometry
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of compounds
 Wavelength Shifts
• The effect of conjugation
• One of the best ways to bring about a bathochromic shift (Red Shift) is to increase
the extent of conjugation in a double-bonded system.
• In the presence of conjugated double bonds, the electronic energy levels of a
chromophore move closer together. As a result, the energy required to produce a
transition from an occupied electronic energy level to an unoccupied level decreases,
and the wavelength of the light absorbed becomes longer

B=4
A=3
C=5

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 Wavelength Shifts
• The effect of conjugation on alkenes
• The bathochromic shift that results from an increase in the length of a
conjugated system implies that an increase in conjugation decreases
the energy required for electronic excitation
• The energy gap dividing the bonding and antibonding orbitals becomes
progressively smaller with increasing conjugation.

Arrows indicate the HOMO–LUMO

transitions. The increased
conjugation shifts the observed
wavelength of the absorption to
higher values.

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 Woodward-Fieser Rules
• Calculating wavelengths for Dienes
• In general, conjugated dienes exhibit an intense band (e = 20,000 to
26,000) in the region from 217 to 245 nm
• Generally, alkyl substitution produces bathochromic shifts and
hyperchromic effects. However, with certain patterns of alkyl
substitution, the wavelength increases but the intensity decreases

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 Woodward-Fieser Rules
• Calculating wavelengths for Dienes

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 Woodward-Fieser Rules
• Calculating wavelengths for Dienes

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 Woodward-Fieser Rules
• Calculating wavelengths for Conjugated Carbonyl Compounds

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 Woodward-Fieser Rules

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 Woodward-Fieser Rules

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 Woodward-Fieser Rules

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 Woodward-Fieser Rules
• Example 1

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 Woodward-Fieser Rules
• Example 2

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 Woodward-Fieser Rules
• Example 3

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 Aromatic Compounds
2. Substituent Effects
a. Substituents with Unshared Electrons
• 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
Substituent 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
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 Aromatic Compounds
2. Substituent Effects
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 50

with the addition of the n  * transition and ring size
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 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”

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 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

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 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 53
indigo!

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 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

CH3 CH3
N H
O3S N N NN N
CH3 O 3S CH3

Yellow, pH > 4.4 Red, pH < 3.2

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