Color Chemistry

Dr. Vincent Chi-Chiu KO

Department of Biology and Chemistry

City University of Hong Kong

Color Chemistry 1
 The Electromagnetic Spectrum

Color Chemistry 2
 UV-Visible Spectroscopy
Near UV 200 – 380 nm
Visible 380 – 780 nm
(Vacuum UV ~ 100 – 200 nm)
- UV-visible radiation comprises only a small part
of the electromagnetic (EM) spectrum
- energy region appropriate for electronic transition
freq. (Hz.)
E = h velocity of light (ms–1)
=h
c

(nm)
_  10–9m
= hc
wavenumber (cm–1)
Color Chemistry 3
Color Chemistry 4
Color Chemistry 5
 Electronic Transition
- promotion of an electron from a lower energy orbital to
a higher energy orbital (energy is quantized)

Color Chemistry 6
 Atomic Absorption

Color Chemistry 7
 Emission vs. Absorption

h
Absorption

h’
Emission +

Color Chemistry 8
 Atomic Emission

Color Chemistry 9
 Flame Test

Color Chemistry 10
 Fireworks

Color Chemistry 11
 Atoms - line spectrum

Molecules - bands rather than lines

- Many levels as there are many different atoms or
atoms with different chemical environment

Color Chemistry 12
 Classification of Electronic Transitions
- according to the nature of the orbitals involved

  * alkenes, alkynes, aromatics, multiple bonded

compounds
n  * carbonyl, thiocarbonyl, nitro, azo, imine, nitrile
n  * amines, alcohols, ethers, thiols, thioethers, haloalkanes
  * alkanes

* e.g. x
n  *
*
_
S + + z
n  * pz
n y
   *
hybridization
  *
   

two sp hybrid orbitals

Color Chemistry 13
 Classification of Electronic Transitions
- according to the nature of the orbitals involved

  * alkenes, alkynes, aromatics, multiple bonded

compounds
n  * carbonyl, thiocarbonyl, nitro, azo, imine, nitrile
n  * amines, alcohols, ethers, thiols, thioethers, haloalkanes
  * alkanes

*
n  *
*
n  *
n In general, transition energy:
   *   * > n  * >   * > n  *
  *


Color Chemistry 14
 e.g.   * transition of H2C=CH2

+ + +
H H h H H
C C C C
H H H H
+
pz pz nodal plane

C + + C C + C +

sp2 sp2
nodal plane

Color Chemistry 15
 6
4 4
* * * 5 *
LUMO
3 LUMO 3
4 LUMO
pz pz 2 3 HOMO
2 HOMO
HOMO    
2
1 1
1

H2C CH2

Greater extent of conjugation

 lower   * transition E  longer max

(larger max)

Color Chemistry 16
Color Chemistry 17
 The energies of the orbitals that are formed when N atoms are brought up to form a line

Color Chemistry 18
 CC chromophore

H(CC)4H H(CC)6H H(CC)8H

max: 226 nm < 275 nm < 316 nm

C=O chromophore

- n  * transition
-   * transition
O
e.g. Acetone max (hexane)
H3C CH3 279 nm
(n  *)
188 nm
(  *)

Color Chemistry 19
 (ii) Biphenyls and binaphthyls

- biphenyl is not coplanar

Me (2 rings approx. 45)

- 2-subst. biphenyl even

less coplanar

max (EtOH)
250 nm 237 nm
( 19,000) ( 10,250)

Color Chemistry 20
 Me Me

- identical max
Me Me Me Me
(probably 2 rings approx.
Me Me
90)

Me

max (EtOH)
266 nm 266 nm
( 545) ( 260)

Color Chemistry 21
 H H H
C C
C C H
H H

cis- trans-
coplanarity destroyed more effective - orbital
“loss” of conjugation overlap
(shorter max and
smaller max)

283 nm 320 nm

Color Chemistry 22
 Photochromism
Light (h1)

A B
Light (h2)

If the absorption properties (colors) of A and B are different, these photoswitchable

molecules are known as photochromic compounds

UV

UV VIS

VIS

O O
N F F F F
N
F F F F
O
O
O F F h1 F F
O
O O
R R h2
S S R S S R
Color Chemistry 23
 UV

UV UV

Yellow Red

Color Chemistry 24
 Application in Sunglasses
Photochromic glasses

Color Chemistry 25
 OH h1
N
+N OH
NO h2,  N

O
Colorless Dark Blue

Color Chemistry 26
 Photochromic Windows

Color Chemistry 27
 Photochromic Dyes and Pigments

Photochromic Toy Photochromic T-shirt

Photochromic Ink
Color Chemistry 28
 Application in Security and Sensor

UV Sensor

Security Ink

Color Chemistry 29
 Application in Optical Data Storage
h1
A B
1 h2

0
A and B represent two states,
1
ON and OFF (1 and 0)
0
Can be used as binary storage
0

1 The difference in the optical

properties such as absorptivity,
1
refractivity, luminescence, etc,
1 could be used for reading out

Color Chemistry 30
 Thermochromism
Heating
A B
Cooling

Color Chemistry 31
 Thermochromic Compounds
Example:
O O
S S
* *
S S
O O
At low temperature, the polymer
structure is planar.
S
 Fully -conjugated
O
n  Absorption in low energy
 Violet in color

Cool Heat

At high temperature, the polymer

S O S O S structure becomes non-planar.
* S S *

O O O n
 Less -conjugated
 Absorption in high energy
 Yellow in color

Color Chemistry 32
 Electrochromism
Oxidation
A B
Reduction

Color Chemistry 33
 Emission vs. Absorption

h
Absorption

h’
Emission +

Color Chemistry 34
 Luminescent Compounds

Color Chemistry 35
 Measurement

Color Chemistry 36
 Luminescent Sensors

The presence of O2 would

destroy the luminescence

The presence of the target

compound would increase the
luminescent signals

Color Chemistry 37
 Luminescent Imaging

Color Chemistry 38
 Chemiluminescence
Cl Cl
O Cl
C O
Cl O C
+ H2O2 + F
COOC 5 H11 O
C5 H11OOC Cl
Cl

Cl Cl

+ 2CO2 + *F
Cl OH
COOC 5 H11

Color Chemistry 39
 Applications in Forensic Science

Blood
Detection

Color Chemistry 40
 Fingerprint Detection

Color Chemistry 41
 OLED

Color Chemistry 42
 OLED Displays

Color Chemistry 43