Photochromism and Piezochromism

Blake Connolly 27/05/2014

Introduction
The purpose of this experiment was to synthesize 2,2',4,4',5,5'-hexaphenyl-4H,4'H-4,4'-biimidazole
from oxidative coupling of 2,45-triphenyl-1H-imidazole and analyse the photochromic and
piezochromic properties.
Experimental
2,1,5-triphenyl-1H-imidazole (0.97g 0.003mol) was added to ethanol (100ml) follower by potassium
hydroxide pellets (8.09g 0.144mol) and water (5ml). The solution was mixed until a clear. The
solution was cooled to 5
0
C and a mixture of water (250ml), potassium ferricynanide (3.15g,
0.009mol) and ethanol (100ml) was added periodically not allowing the reaction not to exceed 10
0
C.
The precipitate was filtered and washed with 5 x 50ml of water and 10ml of 50% aqueous ethanol.
The product was then thoroughly dried. Yield (0.96g 106%) Observed m.p. 263
0
C (decomp.)
Results & Discussion

The melting point observed differs significantly from literature vale of 187.5-188.5
0
C
[1]
. This is
thought to be due to some unreacted 2,4,52,45-triphenyl-1H-imidazole (m.p. 274-276
0
C)
[2]
. Another
reason could be due to the product being slightly wet. This reason would also explain the yield.The
UV-Vis of the product obtained (conc. 2.7mm 400nm - 700nm) peaked at 553nm (0.03A) for the
product before irradiation and 554nm (0.46A) after irradiation. It can be seen clearly that after
irradiation the absorbance of the product drastically increases, it was also noticed that upon irradiation
the solution turned an purple colour. The product when ground turned a dark purple colour and upon
removal and storage in the dark it slowly reverted to a light purple/grey similar to a combination of
both. The coloured species is a reactive intermediate in this case a free radical formed by the cleavage
of the two five-membered ring.

NMR - Dimer 4
1
H
13
C

Chemical
Shift (ppm)

No. of
Hydrogens

Multiplicity

Assignment

Chemical
Shift (ppm)

Assignment

7.26

30

multiplet

Benzene Ring

126.13
Aromatic

4

1



Ethanol

127.08

Aromatic

1.75

2



Water

127.47

Aromatic

1.25

2



Ethanol

127.49

Aromatic


127.57

Aromatic
127.73 Aromatic
127.79 Aromatic
127.97 CN
3
Ph
128.34 Aromatic
129.27 Aromatic
130.23
131.02
132.01















NMR Dimer 3
1
H
13
C

Chemical
Shift (ppm)

No. of
Hydrogens

Multiplicity

Assignment

Chemical
Shift (ppm)

Assignment

7.26

30

multiplet

Benzene Ring

126.13

Aromatic

4

1



Ethanol

127.08
Aromatic

1.75

2



Water
127.47
127.49
Aromatic
Aromatic

1.25

2



Ethanol
127.57
127.73
Aromatic
Aromatic








127.79
128.34
Aromatic
Aromatic
129.27 Aromatic
130.23
131.02
132.01








Questions

1)
The radical formed has the ability to stabilise itself through resonance structures localising the
electrons within the ring.




2)
see attached page.



3)


4)
Photochromic materials are useful in today's society. One use of these are in transition lenses
whereby when the wearer is in the sun they darken and vice-versa. Piezochromic materials change
colour when a force is applied to it. A method is currently being researched for the use of
piezochromic ink in preparation of bank notes as to prevent forgeries.






Conclusion

Reference List

White; Sonnenberg
Journal of the American Chemical Society, 1966 , vol. 88, p. 3825,3828
Teimouri, Abbas; Chermahini, Alireza Najafi
Journal of Molecular Catalysis A: Chemical, 2011 , vol. 346, # 1-2 p. 39 - 45
http://www.google.com/patents/US20070259286