Lecture 6

CHEM F313

UV-Vis Spectroscopy
06-11-21
 RECAP
CHROMOPHORE: • Chromophore, is thus defined as any functional group that absorbs electromagnetic radiation.

AUXOCHROME: • Originally defined as: A group that could enhance the color imparting properties of a chromophore
without being itself a chromophore. Example: -OR, -NH2, -NR2, etc.
• Auxochrome can be a saturated or unsaturated group with non-bonding electrons that helps in
extending the conjugation of a chromophore.

Example from Nature: Green Color of Chlorophylls

UV-Visible Spectroscopy: Key Points

Types of electrons available for electronic transitions:

Lambert-Beer’s law
(i) Allowed transitions (ii) Forbidden transitions

Absorption Characteristics of Some Common Chromophores

 Ultraviolet Spectroscopy

• 200-400 nm photons excite electrons from a  bonding orbital to a

* anti-bonding orbital.
• Conjugated dienes have MO’s that are closer in energy.
• A compound that has a longer chain of conjugated double bonds
absorbs light at a longer wavelength.
 Conjugated systems:

C C

LUMO

HOMO

• Preferred transition is between Highest Occupied Molecular Orbital (HOMO) and Lowest
Unoccupied Molecular Orbital (LUMO).
• Additional conjugation (double bonds) lowers the HOMO-LUMO energy gap.
 For Compounds with Multiple Chromophores:

If isolated (more than one single bond apart)

- e are additive
- l constant

CH3CH2CH2CH=CH2 l max= 184 e max = 10,000

CH2=CHCH2CH2CH=CH2 l max=185 e max = 20,000

If conjugated - shifts to higher l’s (red shift)

1,3 butadiene: l max= 217 nm ; emax= 21,000

1,3,5-hexatriene l max= 258 nm ; emax= 35,000

 Similar structures have similar UV spectra

O
O

l max = 238, 305 nm l max = 240, 311 nm l max = 173, 192 nm

 UV Spectral Nomenclature

Terminology for Absorption Shifts

Nature of Shift Descriptive Term

To Longer Wavelength Bathochromic Blue Shift Red Shift
To shorter wavelength To longer wavelength
To Shorter Wavelength Hypsochromic
To Greater Absorbance Hyperchromic
To Lower Absorbance Hypochromic
 Solvents for UV
(showing high energy cutoffs)
Water 205 Dioxane 220
CH3CN 210 THF 220
C6H12 210 CH2Cl2 235
Ether 210 CHCl3 245
EtOH 210 CCl4 265
Hexane 210 benzene 280
MeOH 210 Acetone 300

Various buffers for HPLC, check before using.

 Solvent Effects - Intensity
Solvents can induce significant changes in the wavelengths and intensity of absorbance.
 Solvent effects

π → π* transitions leads to more polar excited state .

The π* state is more polar and more stabilized in polar solvent relative to the
nonpolar one.

Thus changing from nonpolar to polar solvent there is a red shift or

bathochromic shift.
(Polar solvent - increase in λmax, decrease in ΔE)
 Solvent effects
n → π* transition:

The n state is much more easily stabilized by polar solvent effects (H-bonds and
association).

Thus changing from nonpolar to polar solvent there is a blue shift or hypsochromic shift
(Polar solvent - decrease in λmax, increase in ΔE)

π* π*
n

π π
Nonpolar solvent Polar solvent
in methanol in heptane n→*
methanol

bathochromic
shift
heptane

O
 Isosbestic point

Binding of a lanthanide complex to an

oligonucleotide

- At different pH, the spectrum will be shifted to different lmax, but all spectra
intersect at certain l which is known as isosbestic point

- At isosbestic point, the same absorbance is given for the same concentration
at different pH, i.e. absorbance is not pH dependent but concentration
dependent
In spectroscopy, an isosbestic point is a specific wavelength,
wavenumber or frequency at which the total absorbance of a sample does
not change during a chemical reaction or a physical change of the sample.
 Electronic Transition: Selection Rules

In electronic spectroscopy the following selection rules determine whether or not

transitions are formally allowed:
1. Spin selection rule: ΔS = 0
Allowed transitions: singlet → singlet or triplet → triplet
Forbidden transitions: singlet → triplet or triplet → singlet
Changes in spin multiplicity are forbidden
 Electronic Transition: Selection Rules

2. Laporte (orbital) selection rule: there must be a change in the parity

(symmetry) of the molecular orbital
Laporte-allowed transitions: g → u
Laporte-forbidden transitions: g → g or u → u

g stands for gerade – w.r.t. a center of symmetry

u stands for ungerade – w.r.t. a center of symmetry

[Δℓ = ± 1 (ℓ is the azimuthal or orbital quantum number, where ℓ = 0 (s orbital), 1

(p orbital), 2 (d orbital), etc.)

[Allowed transitions: s → p, p → d, d → f, etc.

Forbidden transitions: s → s, d → d, p → f, etc.]
 UV Spectroscopy
Structure Determination
Woodward-Fieser Rules – Cyclic Dienes and Trienes

If one bond is exocyclic to one ring 5 nm

If exocyclic to two rings simultaneously 10 nm

*Solvent effects are minimal here

 UV Spectroscopy
Structure Determination
A. Dienes

For example: 1,2,3,7,8,8a-hexahydro-8a-methylnaphthalene

heteroannular diene = 215 nm

3 alkyl subs. (3 x 5) +15 nm

1 exo C=C + 5 nm
235 nm

Experimental value 235 nm

Examples

c
a b
 UV Spectroscopy

Structure Determination
Woodward-Fieser Rules – Cyclic Dienes and Trienes

If one bond is exocyclic to one ring 5 nm

If exocyclic to two rings simultaneously 10 nm

*Solvent effects are minimal here

 UV Spectroscopy

Structure Determination
A. Dienes

For example: 1,2,3,7,8,8a-hexahydro-8a-methylnaphthalene

heteroannular diene = 215 nm

3 alkyl subs. (3 x 5) +15 nm

1 exo C=C + 5 nm
235 nm

Experimental value 235 nm

Examples

c
a b
 2,4-dimethylpenta-1,3-diene
(Transoid/Heteroannular Diene=215nm)

1-methylcyclohexa-1,3-diene
(Cisoid/Homoannular Diene=253nm)

3-methoxy-10-methyl-2,7,8,9,10,11,12,13,14,15,16,17-dodecahydro-1H-
cyclopenta[a]phenanthrene
(Core- Transoid/Heteroannular Diene=215 nm)
 UV Spectroscopy

Structure Determination
A. Dienes
Woodward-Fieser Rules – Cyclic Dienes

Two common errors to avoid

R
This compound has three exocyclic
double bonds; the indicated bond is
exocyclic to two rings

This is not a homoannular diene; you

would use the base value for an acyclic
diene
10,13-dimethyl-2,3,9,10,11,12,13,15,16,17-
decahydro-1H-cyclopenta[a]phenanthrene
(Core- Transoid/Heteroannular Diene=215 nm)
 Enones

 
b b

b
O 


x 
O
 b
Enones
b
O O O
O
O


x
215 202 227 239
X=H 207 Base Values, add these increments…
 b   ,+
X=R 215 (acyclic or 6 memb)
Extend C=C +30
X=OH, Add exocyclic C=C +5
OR 197
Homoannular diene +39
alkyl +10 +12 +17 +17
With solvent
correction of….. OH +35 +30 +30 +50
Water +8 O-Acyl +6 +6 +6 +6
EtOH 0 O-alkyl +35 +30 +17 +31
CHCl3 -1
NR2 +95
Dioxane -5
S-alkyl +80
Et2 O -7
Cl/Br +15/+25 +12/+30 +15/+25 +15/+25
Hydrocarbon -11
 Enones

STRUCTURE DETERMINATION
2. Woodward-Fieser Rules - Enones
Some examples – keep in mind these are more complex than dienes
β O cyclic enone = 215 nm
2 x β- alkyl subs. (2 x 12) +24 nm
239 nm

Experimental value 238 nm

cyclic enone = 215 nm

extended conj. +30 nm
β-ring residue +12 nm
δ-ring residue +17 nm
exocyclic double bond + 5 nm
279 nm

Experimental 280 nm
 3,4-dimethylpent-3-en-2-one
Core- cyclopentenone
(Core- α,β-unsaturated ketone=215nm)

Core- cyclohexenone
Core- Homoannular/Cisoid diene
 Carbonyl Group
1. General Features
Carbonyls have two primary electronic transitions:

*
Remember, the  → * transition is allowed and
gives a high ε, but lies outside the routine range of
UV observation
n
The n → * transition is forbidden and gives a very
low ε, but can routinely be observed


 Carbonyl Group
1. General Features
With auxochromic substitution on the carbonyl, pronounced hypsochromic shifts
are observed for the n → π* transition (λmax):

This is explained by the inductive withdrawal of electrons

293 nm by O, N or halogen from the carbonyl carbon – this causes
the n-electrons on the carbonyl oxygen to be held more
235 firmly

214 It is important to note this is different from the

auxochromic effect on π → π* which extends conjugation
204 and causes a bathochromic shift. In most cases, this
bathochromic shift is not enough to bring the π→ π*
204
transition into the observed range
A comparison of →* energy gap in a series of polyenes of increasing chain length
 Enones
STRUCTURE DETERMINATION s* (anti-bonding)

* (anti-bonding)
General Features
If the C=O system is conjugated both the n → π* and π → π*
bands are bathochromically shifted n (non-bonding)

Here, several effects must be noted:

 (bonding)
❖The effect is more pronounced for π → π*

❖If the conjugated chain is long enough, the much higher

intensity π → π* band will overlap and drown out the n → π*
band

❖The shift of the n → π* transition is not as predictable

For these reasons, Empirical Woodward-Fieser rules for

conjugated enones are for the higher intensity, allowed π → π*
transition