Electronic Spectroscopy

Ultraviolet and visible

Where in the spectrum are these
transitions?



Why should we learn this stuff?
After all, nobody solves structures with
UV any longer!
Many organic molecules have chromophores that absorb UV
UV absorbance is about 1000 x easier to detect per mole than NMR
Still used in following reactions where the chromophore changes. Useful
because timescale is so fast, and sensitivity so high. Kinetics, esp. in
biochemistry, enzymology.
Most quantitative Analytical chemistry in organic chemistry is conducted using
HPLC with UV detectors
One wavelength may not be the best for all compound in a mixture.
Affects quantitative interpretation of HPLC peak heights
Uses for UV, continued
Knowing UV can help you know when to be skeptical of quant results. Need
to calibrate response factors
Assessing purity of a major peak in HPLC is improved by diode array data,
taking UV spectra at time points across a peak. Any differences could suggest a
unresolved component. Peak Homogeneity is key for purity analysis.
Sensitivity makes HPLC sensitive
e.g. validation of cleaning procedure for a production vessel
But you would need to know what compounds could and could not be detected
by UV detector! (Structure!!!)
One of the best ways for identifying the presence of acidic or basic groups, due
to big shifts in for a chromophore containing a phenol, carboxylic acid, etc.

bathochromic shift hypsochromic shift
The UV Absorption process
o o* and o t* transitions: high-energy,
accessible in vacuum UV (
max
<150 nm). Not usually
observed in molecular UV-Vis.
n o* and t o* transitions: non-bonding electrons
(lone pairs), wavelength (
max
) in the 150-250 nm region.
n t* and t t* transitions: most common
transitions observed in organic molecular UV-Vis,
observed in compounds with lone pairs and multiple
bonds with
max
= 200-600 nm.
Any of these require that incoming photons match in
energy the gap corrresponding to a transition from
ground to excited state.
Energies correspond to a 1-photon of 300 nm light are
ca. 95 kcal/mol
What are the
nature of these
absorptions?
Example: t t* transitions responsible for ethylene UV absorption at ~170 nm
calculated with ZINDO semi-empirical excited-states methods (Gaussian 03W):
HOMO t
u
bonding molecular orbital
LUMO t
g
antibonding molecular orbital
hv 170nm photon
Example
for a
simple
enone


n


n
*


n
* *
*
*
*
* *
*
t-t*;
max
=218
c=11,000
n-t*;
max
=320
c=100
How Do UV spectrometers work?
Two photomultiplier
inputs, differential
voltage drives amplifier.
Matched quartz cuvettes
Sample in solution at ca. 10
-5
M.
System protects PM tube from
stray light
D2 lamp-UV
Tungsten lamp-Vis
Double Beam makes it a
difference technique

Rotates, to
achieve scan
Diode Array Detectors
Diode array
alternative puts
grating, array of
photosens.
Semiconductors after
the light goes through
the sample.
Advantage, speed,
sensitivity,
The Multiplex
advantage
Disadvantage,
resolution is 1 nm, vs
0.1 nm for normal
UV
Model from Agilent literature. Imagine
replacing cell with a microflow cell for
HPLC!
Experimental details
What compounds show UV spectra?
Generally think of any unsaturated compounds as good
candidates. Conjugated double bonds are strong absorbers
Just heteroatoms are not enough but C=O are reliable
Most compounds have end absorbance at lower frequency.
Unfortunately solvent cutoffs preclude observation.
You will find molar absorbtivities c in Lcm/mol, tabulated.
Transition metal complexes, inorganics
Solvent must be UV grade (great sensitivity to impurities with
double bonds)
The NIST databases have UV spectra for many compounds
An Electronic Spectrum
A
b
s
o
r
b
a
n
c
e

Wavelength, , generally in nanometers (nm)
0.0
400 800
1.0
200
UV Visible

max
with certain
extinction c

Make solution of
concentration low enough
that A 1
(Ensures Linear Beers
law behavior)
Even though a dual beam
goes through a solvent
blank, choose solvents
that are UV transparent.
Can extract the c value if
conc. (M) and b (cm) are
known
UV bands are much
broader than the photonic
transition event. This is
because vibration levels
are superimposed on UV.
Solvents for UV (showing high
energy cutoffs)
Water 205
CH
3
CN 210
C
6
H
12
210
Ether 210
EtOH 210
Hexane 210
MeOH 210
Dioxane 220
THF 220
CH
2
Cl
2
235
CHCl
3
245
CCl
4
265
benzene 280
Acetone 300
Various buffers for
HPLC, check before
using.

Organic compounds (many of
them) have UV spectra
From Skoog and West et al. Ch 14
One thing is clear
Uvs can be very non-specific
Its hard to interpret except at a
cursory level, and to say that the
spectrum is consistent with the
structure
Each band can be a
superposition of many
transitions
Generally we dont assign the
particular transitions.
An Example--Pulegone
Frequently
plotted as
log of
molar
extinction
c
So at 240 nm,
pulegone has
a molar
extinction of
7.24 x 10
3
Antilog of 3.86

O
Can we calculate UVs?
Electronic Spectra
Wavelength (nm)
Molar Absorptivity (l/mol-cm)
220 230 240 250 260 270 280 290 300
0
10049
20097
30146
40194
50243
nacindolA
Electronic Spectra
Wavelength (nm)
Molar Absorptivity (l/mol-cm)
220 230 240 250 260 270 280 290 300
0
10394
20789
31183
41578
51972
Nacetylindol
Semi-empirical (MOPAC) at
AM1, then ZINDO for
config. interaction level 14
Bandwidth set to 3200 cm
-1
The orbitals involved
Electronic Spectra
Wavelength (nm)
Molar Absorptivity (l/mol-cm)
200 210 220 230 240 250 260 270 280 290 300
0
11097
22195
33292
44390
55487
Nacetylindol
Showing
atoms whose
MOs
contribute
most to the
bands
The Quantitative Picture
Transmittance:
T = P/P
0
B(path through sample)
P
0
(power in)

P
(power out)

Absorbance:
A = -log
10
T = log
10
P
0
/P
The Beer-Lambert Law (a.k.a. Beers Law):
A = cbc
Where the absorbance A has no units, since A = log
10
P
0
/ P
c is the molar absorbtivity with units of L mol
-1
cm
-1
b is the path length of the sample in cm
c is the concentration of the compound in solution, expressed in mol L
-1
(or M, molarity)
Beer-Lambert Law
Linear absorbance with increased concentration--directly
proportional
Makes UV useful for quantitative analysis and in HPLC
detectors
Above a certain concentration the linearity curves down,
loses direct proportionality--Due to molecular associations
at higher concentrations. Must demonstrate linearity in
validating response in an analytical procedure.
Polyenes, and Unsaturated
Carbonyl groups;
an Empirical triumph
R.B. Woodward, L.F. Fieser and others
Predict
max
for t* in extended conjugation
systems to within ca. 2-3 nm.
Homoannular, base 253 nm
heteroannular, base 214 nm
Acyclic, base 217 nm
Attached group increment, nm
Extend conjugation +30
Addn exocyclic DB +5
Alkyl +5
O-Acyl 0
S-alkyl +30
O-alkyl +6
NR2 +60
Cl, Br +5
Similar for Enones
O
x
o
|
|
O
O
X=H 207
X=R 215
X=OH 193
X=OR 193
215
202
227 239
Base Values, add these increments
Extnd C=C +30
Add exocyclic C=C
+5
Homoannular diene +39
alkyl +10 +12 +18 +18
OH +35 +30 +50
OAcyl +6 +6 +6 +6
O-alkyl +35 +30 +17 +31
NR
2

S-alkyl
Cl/Br +15/+25 +12/+30
o |
o,+
With solvent correction
of..
Water +8
EtOH 0
CHCl
3
-1
Dioxane -5
Et2O -7
Hydrcrbn -11
Some Worked Examples
O
Base value 217
2 x alkyl subst. 10
exo DB 5
total 232
Obs. 237
Base value 214
3 x alkyl subst. 30
exo DB 5
total 234
Obs. 235
Base value 215
2 alkyl subst. 24
total 239
Obs. 237
Distinguish Isomers!
HO
2
C
HO
2
C
Base value 214
4 x alkyl subst. 20
exo DB 5
total 239
Obs. 238
Base value 253
4 x alkyl subst. 20
total 273
Obs. 273
Generally, extending conjugation
leads to red shift
particle in a box QM theory; bigger box
Substituents attached to a chromophore that cause a red shift
are called auxochromes
Strain has an effect

max
253 239 256 248
Interpretation of UV-Visible Spectra
Transition metal
complexes; d, f
electrons.
Lanthanide
complexes sharp
lines caused by
screening of the f
electrons by other
orbitals
One advantage of this
is the use of holmium
oxide filters (sharp
lines) for wavelength
calibration of UV
spectrometers.
See Shriver et al. Inorganic Chemistry, 2
nd
Ed. Ch. 14
Benzenoid
aromatics
From Crewes, Rodriguez, Jaspars, Organic Structure Analysis
UV of
Benzene in
heptane
Group K band (c)
B band(c)
R band
Alkyl 208(7800) 260(220) --
-OH 211(6200) 270(1450)
-O
-
236(9400) 287(2600)
-OCH
3
217(6400) 269(1500)
NH
2
230(8600) 280(1400)
-F 204(6200) 254(900)
-Cl 210(7500) 257(170)
-Br 210(7500) 257(170)
-I 207(7000) 258/285(610/180)
-NH
3
+
203(7500) 254(160)
-C=CH
2
248(15000) 282(740)
-CCH 248(17000) 278(6500
-C
6
H
6
250(14000)
-C(=O)H 242(14000) 280(1400) 328(55)
-C(=O)R 238(13000) 276(800) 320(40)
-CO
2
H 226(9800) 272(850)
-CO
2
- 224(8700) 268(800)
-CN 224(13000) 271(1000)
-NO
2
252(10000) 280(1000) 330(140)
Substituent effects dont really add up
Cant tell any thing about substitution geometry
Exception to this is when adjacent substituents can
interact, e.g hydrogen bonding.
E.g the secondary benzene band at 254 shifts to
303 in salicylic acid
In p-hydroxybenzoic acid, it is at the phenol or
benzoic acid frequency
Heterocycles
Nitrogen heterocycles are pretty similar to the benzenoid
anaologs that are isoelectronic.
Can study protonation, complex formation (charge transfer
bands)
Quantitative
analysis
Great for non-
aqueous titrations
Example here
gives detn of
endpoint for
bromcresol green
Binding studies
Form I to form II
Isosbestic points
Single clear point, can exclude
intermediate state, exclude light
scattering and Beers law applies
Binding of a lanthanide complex to
an oligonucleotide
More Complex Electronic Processes
Fluorescence: absorption of
radiation to an excited state,
followed by emission of
radiation to a lower state of the
same multiplicity
Phosphorescence: absorption of
radiation to an excited state,
followed by emission of
radiation to a lower state of
different multiplicity
Singlet state: spins are paired,
no net angular momentum (and
no net magnetic field)
Triplet state: spins are unpaired,
net angular momentum (and net
magnetic field)