Interlude on Spectroscopy

interaction of radiation with matter

type of interaction depends on the energy of the radiation
use of the full electromagnetic spectrum is possible
interaction happens through absorption
spectrum is a plot of the absorption as a function of the energy used
A

, wavelength

UV/Vis

, wavenumber

IR

, frequency

NMR

Electromagnetic spectrum

high
energy

low
energy

Radiowaves

ionization
M + h M+ + e

molecular rotations
microwave spectroscopy

electronic transitions
UV/Vis
molecular vibrations
IR

nuclear spin transitions

NMR

Chapter 2. Ultraviolet (and visible) spectroscopy

electronic transitions
O

which transitions?
wavelength and intensity, max and
what happens if we change the molecule?
substituent effects on max and
laws for the prediction of max in conjugated alkenes and ketones
Reading:
Pavia
Chapter 7
Dont need 7.13, 7.14D and E, 7.15

1. General
range of radiation: 200 800 nm
absorption leads to excitation of electrons
E

electronically excited state

E: absorbed energy, quantized
electronic ground state of a molecule

Question: How large is the energy gap needed (lets say at 200 nm) and
what does that imply for the population of the two states?
Plancks
law

E = h = h

Boltzmann N u = e
distribution N l

E
kT

= 6.6 10

=e

34

3 108 m / s 109 nm / m
Js
= 9.9 10 19 J
200nm

9.910 19 J
1.3810 23 J / K 298 K

= 0 read: 1 upper over all lower:

all molecules are in
their electronic ground state

2. Nature of electronic excitations

A. Electronic states
electronic levels for the lowest-energy transition are HOMO and LUMO
E

LUMO

HOMO
ground
state

excited
state

E is quantized: only a specific E leads to this promotion

we should observe a line spectrum

true for an atom, but not for a molecule
a molecule vibrates and rotates

2. Nature of electronic excitations continued

A. Electronic states
every electronic state possesses vibrational and rotational states

: nm

cm

Rotationallevels

E
Rotationallevels

2. Nature of electronic excitations continued

A. Electronic states

leads to line broadening: all E are similar but slightly different

A

max
(wavelength for
maximum
absorption)

max
observed band
due to poor
resolution

2. Nature of electronic excitations continued

B. Molecular orbitals
occupied MOs n

unoccupied MOs

general orbital diagram

E

*
*
n

possible transitions:
n *
n *
*
E
*
*
*

molecules?

3. Selection rules
govern which transitions are allowed, which forbidden
allowed transition is observed
forbidden transition is either not observed or very weak
h

the promoted electron does not change spin

singlet

only one electron is excited

transitions between orbitals of different symmetry are forbidden

: different symmetry

* allowed
n * forbidden, but observed

singlet

4. Chromophores
group of atoms that makes an absorption possible (at least two)

important chromophores

less important chromophores

(first max too small/short)

R2C=O, R2C=S, R2C=N-R

R-OH, R-O-R, R-NH2

R-N=N-R

R2C=CR2, R-CC-R, R-CN

R-NO2
O

, R

, R

R
OH

OR

NH2

(aromatics in general)
see Table 7.3

4. Chromophores continued
probably the best-studied chromophore is the carbonyl group

280-290 nm
but
forbidden,
low intensity

180-190 nm
allowed,
high intensity,
but too short to be observed!

4. Chromophores continued
typical UV-Vis spectrum of a carbonyl compound

What is this?
C=O plus C=C?

n *

235 nm

315 nm

189 nm

280 nm

* becomes observable

4. Chromophores continued
the combination of chromophores leads to shifts in band
intensity: increased: hyperchromic effect
decreased: hypochromic effect
wavelength: increased: longer max:

decreased: shorter max:

- bathochromic effect

- hypsochromic effect

- red shifted * band

- blue shifted n * band

- less energetic light

- more energetic light

- through conjugation

- through heteroatoms

O
C

O
C

C
C

1,max < 2,max

A

217

1,max > 2,max

O

175

[nm]

O
OH

204 293

[nm]

4. Chromophores continued
reason for a red shifted * band through conjugation:
HOMO LUMO gap becomes smaller upon conjugation
acyclic conjugated:
MO (interaction) diagram for the -orbitals of ethene and butadiene
LCAO principle: linear combinations of atomic orbitals (p only)
3 nodes

*4
*

1 node

E1

pC

C C

*
2 nodes

1 node

E2

pC

no node

*3

no node

1
C C

C C C C

C C

4. Chromophores continued
the red shift through conjugation can be dramatic:

A
B
C

-carotene
2

C40H56: U = 40 + 1 (56 0) = 41 28 = 13, 11 conjugated C=C max 465 nm

orange!

4. Chromophores continued
reason for a red shifted * band through conjugation
reason for a blue shifted n * band through heteroatoms:
inductive effect: energy of nO is lowered
* still shows a bathochromic shift:

-system is still extended through the heteroatom

O
C

O
C

n * 1,max > 2,max

* 1,max < 2,max

5. Absorption
follows the Lambert-Beer law

I
A = log 0 = cl
I
is determined by the size of the absorbing system
probability of the transition

< 1000 log 2-3: low intensity absorption

>> 1000 log 4-5: high intensity absorption
plotted is A or or log

sample

solvent

I0

6. Materials
Central question: Where does the material absorb?
solvent: - should be transparent in the region of interest
- ideal UV-Vis spectrum:
A

200

800 [nm]

short-wavelength cutoff: H2O, CH3CN 190 nm

CHCl3
240 nm
cuvette: quartz, transparent to 200 nm
polymer, transparent to 220 nm (PMMA)
optical glass, transparent to only 350 nm

see Table 7.1

7. Spectrometer
Beam in a UV-Vis spectrometer
grating
Vis

UV

movable parts

http://teaching.shu.ac.uk/hwb/chemistry/tutorials/molspec/uvvisab3.htm

Diode-array spectrophotometer

no movable parts:
faster
http://www.gmi-inc.com/Categories/spectrophotometers.htm

8. Spectrum
UV-Vis spectra are often not published
x-y data of the extrema are reported instead
Info from this spectrum reported:

max 230 nm log 4.2

272
3.1
282
2.9
Info from this spectrum gained:
- no long-wavelength absorption:
not highly conjugated
- longer-wavelength low intensity:
probably forbidden, possibly n *
- shorter-wavelength high intensity:
probably allowed, possibly *

9. Prediction of max of * transitions

I. Dienes and higher conjugated C=C
Why do we write
acyclic dienes
butadiene

s-trans

and not

? Conformation matters!

4
3
230 nm
2
1

s-cis

271 nm

Interesting, but s-cis is not usually important in acyclic systems!

cyclic dienes
transoid

cisoid

use Woodward-Fieser rules to predict max

9. Prediction of max of * transitions continued

R.B. Woodward
Nobel Prize 1965

I. Dienes and higher conjugated C=C

Woodward-Fieser rules
calculate max from a base value

base value [nm]

acyclic (s-trans)

transoid

cisoid

214

214

253

plus increments for structural features

increment [nm]

another
conjugated C=C

alkyl group or
ring residue

exocyclic C=C

30

plus increments for other substituents

see Table 7.5

9. Prediction of max of * transitions continued

I. Dienes and higher conjugated C=C
Examples
214 + 5 = 219 nm

Colour code:
base system

214 + 30 = 244 nm

increments

214 + 2x5 + 5 = 229 nm

not important
for absorption

214 + 3x5 + 5 = 234 nm

OCH3

234 + 6 = 240 nm
OCH3

9. Prediction of max of * transitions continued

I. Dienes and higher conjugated C=C
Examples
253 + 2x5 = 263 nm

253 + 4x5 + 2x5 = 283 nm

Colour code:
base system
increments
not important
for absorption

253 + 2x30 + 5x5 + 3x5 = 353 nm

9. Prediction of max of * transitions continued

II. Enones and higher conjugated C=O (ketones only)
Woodward rules
calculate max from a base value
O

base value [nm]

acyclic (s-trans)

6-membered ring

5-membered ring

215

215

202
O

plus increments for structural features

increment [nm]

another
conjugated C=C

alkyl group or
ring residue

exocyclic
C=C

homocyclic
(cisoid) diene

30

in 10
in 12
in 18

39

plus increments for other substituents

see Table 7.7

9. Prediction of max of * transitions continued

II. Enones and higher conjugated C=O
Examples
O

215 + 10 + 12 = 237 nm

Colour code:
O

215 + 30 + 10 = 255 nm

215 + 12 = 227 nm
O

215 + 30 + 39 + 18 = 302 nm

202 + 12 = 214 nm

202 + 30 + 12+ 18 + 5 = 267 nm

base system
increments
not important
for absorption

9. Prediction of max of * transitions continued

III. Aromatic compounds
good chromophore: 3 conjugated C=C, cis, in one ring
second primary band, allowed transition, usually not observed
primary band, forbidden transition

secondary band, forbidden transition

often vibrational fine structure

conjugation effects as discussed earlier

Read
7.14
by yourself,
focus on conjugation
issues

no quantitative treatment: max not easy to predict for substitution

Example
An alkene C12H16 and an unsaturated ketone C11H14O, both almost identical in
structure (

), show UV absorptions at 269 and 286 nm, respectively.

Give their structures.