Colour and Constitution

3.
5 Colour and Constitution

3.5.1 Introduction
(1) Early Theories
(2) Modern Theories
(3) Experimental Observation Monoazo Dyes
(4) Application of VB and MO Theories
Rationalisation of colour
VB Theory
MO Theory
1. Qualitative MO Theory - Dewars Rules
2. Quantitave MO Theory PPP Model
Tinctorial Strength
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3.5 Colour and Constitution

3.5.2 Early Theories
1865 : Kekule, Benzene structure
1867 : Graebe and Liebermann, Unsaturated theory
1876 : O. N. Witt's chromophore / auxochrome theory
1879 : Nietzki, Nietzki's Rule
1887 : Armstrong, Quinonoid theory
1900 : Gomberg / Baeyer, Halochromism
1904 : Baly, Isoropesis
1907 : Baeyer / Hantzsch, Conjugated theory (Hewitts Rule)
1914 : Watson Tautomeric theory
1914 : Adams, Rosenstein, Electron oscillation
1916 : Lewis, selective absorption of light
1928 : Dilthey and Wizinger
1935 : Bury, Resonance Theory against Baeyers
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Chromphore Theory
Quinonoid Theory
Resonance Theory
Chromphore Theory ( )

.
Chromophore ; N=N-, -N=O, -NO2, -C=O, -C=C Auxochrome ; OH, -NH2, -NHCH3, -COOH, -SO3H
Chromogene
Auxochrome
Cl
C2H5
N
Dye
O2N
C2H4OH
Chromophore
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Chromphore Theory
Quinonoid Theory
Resonance Theory
Quinonoid Theory ( )
o-quinone p-quinone
,
Tautomerism quinone

O
OH
O
OH
OH
OH
p-Benzoquinone
Hydroquinone
o-Benzoquinone
Catechol
(Yellow)
(Colorless)
(Red)
(Colorless)
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Resonance Theory ( )
.
.
H2N
NH2Cl
NH2
Ph
O
Doebners violetTautomeric form

By Baeyer
(94), (95A)
Ph
O
Cl H2N
Electron oscillation
CO2
H2N
(95), (95A)
H2N
NH2
Ph
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(96),(96A)
By Adams, Rosenstein
CO2
NH2
Resonance Theory
Bury-against Baeyers
Ph
3.5.3 Modern Theories

Two modern theories
VB (Valence bond) theory / MO (Molecule orbital) theory
VB Theory Bonding valence electron pair is localized
between specific atoms
* Schrodinger : Quantum Theory, (H, H2+), Heitler..
* Qualitative / Quantitative VB Theory , Bury Resonance Theory
MO Theory Electron being distributed amongst a set of
molecular orbitals of discrete energies
* LOAO-MO Theory, Hund..
* Huckel : MO(HMO)
* Kukn : Free Electron MO(FEMO)Model
* Dewar : PMO Theory
* Roothaan : Liner Combination Atomic Orbital(LCAO) MO Theory
* PPP Model : High Occupied to Lowest Unoccupied (HO/LU)MO
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Electron Theory

Electron Theory ( )
.
(Eg)

(Ee) (E)
.
E = Ee Eg = h, = c /
.
E=167-297 kJ/mole

Ee; / Ee;
.
(
Eg )
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Electron Theory

Conjugated double bond
Bathochromic shift
4 *
Antibonding
Molecular orbitals
* LUMO
Energy
3* LUMO
excitation
excitation
2 HOMO
HOMO
Bonding
Molecular orbitals
1
CH2=CH2
CH2=CHCH=CH2
Excitation energy of ethylene vs. 1,3-butadiene

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3.5.4 Experimental Observations

Monoazo Dyes
Monoazo Dye - Derivatives of 4-Aminoazobenzene
simple Azobenzene (pale yellow)
introduction of EWG minor effect on the colour
introduction of EDG bathochromic (Table 3.7)
4-NN dimethylamino (deep yellow)
the greater the electron donating power, the more bathochromic
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Table 3.7. Effect of electron-accepting and electron-donating groups of azo-benzene
R1
R
H
H
H
NO2
H
H
H
H
H
Me
MeO
NH2
NH2
NMe2
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R1
H
CO2Me
NO2
NO2
Me
MeO
NH2
NMe2
NEt2
NMe2
NMe2
NMe2
NH2
NMe2
N
N
maxEtOH(nm)
320
325
332
338
333
349
385
407
415
407
407
410
399, 435s
460
R
max
21,000
21,900
24,000
22,900
23,400
26,000
24,500
30,900
29,500
33,900
33,100

EWG into the diazo ring & EDG in the coupling ring
effect of conjugation
meta
para
ortho
N
N
A
D
OH
NH2
NEt2
NEt2
NEt2
NEt2
NEt2
NEt2
NEt2
p - NO2
p - NO2
p - NO2
o - Cl
m - Cl
p - Cl
o - CN
m - CN
p - CN
maxEtOH(nm)
386
439
486
427
423
422
462
446
466
max
29,500
27,400
34,000
29,500
29,800
26,700
30,000
28,100
32,700
Table 3.8. Combined effect of electron-donating and accepting

groups in azo benzene
3.5 Colour
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and Constitution

Electron-withdrawing groups in ring C hypsochromic
(tinctorial strength)
O2N
N
C
O2N
NEt2
N
N
NH2
Y
Y
maxEtOH (nm)
max
H
Cl
CN
NO2
CF3
486
472
472
470
467
-14
-14
-16
-19
34,000
33,800
32,400
31,800
31,400
X
H
Cl
NO2
maxEtOH (nm)
439
427
394
max
-12
-45
27,400
25,800
24,900
These dyes have been chosen to minimise steric effects (see 4.5.9)
Relative to X or Y = H
Table 3.9. Effect of electron-accepting groups in the coupling component ring C
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A N
maxEtOH (nm)
A
NC
NC
NEt2
max
478
33,600
495
36,000
500
38,800
503
33,100
515
39,800
562
46,600
CN
Table 3.10.
Effect of several electron

withdrawing groups in ring D
NC
NC
NC
CN
CN
CN
NC
CN
NC
CN
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X
O2N
N
N
NEt2
Y
H
OMe
H
OMe
NHAc
H
H
OMe
OMe
OMe
maxEtOH (nm)
486
501
488
516
530
max
+15
+2
+30
+44
34,000
32,800
22,600b
29,600b
32,600b
Relative to X = Y = H.
Low because of steric hindrance(see 3.5.9).

Table 3.11. Effect of electron-donating groups in ring C
X
O2N
N
N
(98) ( X = H )
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NEt2
O2N
Ac
H N
N
N
NEt2
(99)

Effect of acylamino group in ring C
(intramolecular H-bonding)
X in (98)
H
NHCOCH3
N
max
maxEtOH (nm)
486
511
34,000
47,000
5,000
3,900
482
36,000
4,900
Et
COCH3
v1/2cm-1)
NO2
O2N
N
N
AcHN
NEt2
O2N
OMe
N
N
Br
NEt2
AcHN
Typical violet dye
Typical blue dye
maxEtOH 543nm
maxEtOH 608nm
(100)
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NO2
(101)

Increasing number of substituents (especially NO2) make
dyes dull
heterocyclic diazo components require fewer electron
accepting groups to produce the bathochromic shift
NO2
N
O2N
N
N
Et
N
OH
Me
Me
thiazole
O2N
N
N
N
N(C2H4OAc)2
Me
S
O2N
maxMeOH 593nm
dinitrothiophene dye
N
(102)
maxMeOH 587nm
maxEtOH 614nm
NO2
(104)
O2N
Et
C2H4CO2Me
benzoisothiazole
(103)
N
N
N(C2H4OAc)2
Me
dinitroaniline dye
maxEtOH 513nm
(105)
Seoul National
dyes with heterocycles as coupling components are more

bathochromic, but not studied enough
O2N
N
N
NMe2
(106)
azo dyes from furan and thiophene
coupling components
Y maxEtOH max
O
S
538
546
Seoul National
50,000
O2N
N
N
NMe2
(107)
azo dyes with benzenoid
counterparts
maxEtOH nmmax 33,000

Yellow dyes
obtained when the diazo component is devoid of EWG
photochromic
commercial ones contain EWGs on both sides(109)
Table 3.13. Substituent effect at the terminal amino group
R
Et
Et
Mea
C2H4CN
H
a
R'
Et
C2H4CN
CH2CN
C2H4CN
H
maxEtOH (nm)
486
452
422
432
439
max
34,000
30,900
26,000
30,000
27,400
Data for Et compound is not available.
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3.5.5 Application of VB and MO Theories

The first excited state of azobenzene is charge separated structure
introduction of an EWG has a minor effect
an EDG at ortho or para stabilizes the excited structure
O
N+
N
N
Charge separated structure

(Excited state)
(111A)
N
N
(110A)
N
N
N+R2
(112A)
O
N+
O
N
N
(111)
Uncharged structure
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N
N
(110)
N
N
NR2
(112)

N
N
unfavourable situation with EDG at both sides

failure of VB theory since experimental
results say otherwise(table 3.7)
N+Me2
(113A)
N
N
ortho- and para-cyano dyes

sharing of charge markedly stabilises the excited state
NMe2
(113)
E is reduced and bathochromic shift

N C
N
N
NC
N+Et2
N
N
N+Et2
(114A)
(114B)
E
NC
N
N
NEt2
(114)
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Meta cyano dyes
Not conjugated to the azo group
N
N
NC
N+Et2
(115A)
E
No stabilisation of the excited state

N
N
NC
NEt2
(115)
N
N
N+R2
A'
substituents meta to the dialkylamino group (116A)
(116A)
inductive and mesomeric (resonance) effect

(table 3,9)
A
N
N
NR2
A'
(116)
Seoul National
N
N
substituents ortho to the amino group(117A)
A'
N+R2
inductive effect only

(table 3.9)
(117A)
A'
N
N
NR2
(117)
bathochromic shift caused by introducing a methoxy group into ring D

O
N+
O
OMe
N
N
Et
O
N
O+Me
N
N
Seoul National
Et
C2H4CN
C2H4CN
(97A)
(97B)

the introduction of a methoxy group in the meta position
to the diethylamino group in ring C
stabilise the excited state by sharing the position charge
on the terminal amino nitrogen atom
bathochromic shift
N
N
O2N
N
N
O2N
N+Et2
NEt2
Me+O
MeO
(118)
(118A)
the effective sharing of the negative charge results in a large

bathochromic shift
N
CN
NC
N
N
(119)
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CN
C
+
N Et2
NC
N
(119A)
N C
(119B)

X
the RSE of a heterocyclic ring such

as thiophene or thiazole is less than
that of benzene
more bathochromic
N
N
N+R2
(120A)
A = acceptor
X = CH, N
X
A
N
N
NR2
(120)
sulphur has available vacant 3d orbitals

acceptable resonance structure with more than 8 electrons
N
N
S
O2N
O2N
N
NR2
Seoul National
(121)
S
N
N+R2
(121A)

VB Theory (qualitative)
MO Theory : Qualitative vs. Quantitative
Qualitative MO Theory
(Dewars Rules)
Qualitative MO Theory Dewars Rules

Predicting qualitatively the effect of substituents on the colour of dyes.
x
*
*
*
*
(i)
(ii)
(122)
*
*
*
*
No two starred atoms are adjacent, and

That the number of starred atoms exceeds the number of
unstarred atoms.
Tinctorial Strength
CH2
Quantitative MO Theory
(PPP Model)
x
NR2
Fig. 3.7 Dewars Rules prediction for 4-aminoazobenzene dyes

correct prediction
X incorrect prediction
Dewars Rules
1.
2.
3.
4.
Any E.W.sub. at a starred position, or any E. D.sub. At an unstarred position, should

cause a large hypsochromic shift.
Any E.W.sub. At an unstarred position, or E.D.sub. At starred position, should cause a
smaller bathochromic shift.
Replacing carbon by nitrogen has the same effect as an E.W.sub. At that position.
Any neutral, unsaturated group such as vinyl or phenyl, anywhere, has a bathochromic
effect.
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(Dewars Rules)
Quantitative MO Theory PPP Model

- Only -electron model effect, -electrons are not included
(PPP Model)
- Predicts colour (max) and tinctorial strength
Tinctorial Strength
- electronic picture of ground and excite states
Table 3.14. Experimental and PPP calculated max value for azobenzene and its o-, m-,p-amino derivatives
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1.
(123A)
(123)
2.
3.
(124A)
(124)
1.
N
X
Comparison of the calculated

electron densities in the origin of the
absorption band by highlighting the
donor and acceptor groups.
in first excited state (123A) the
electron density
PPP model vs. VB theory
-azo N
-azo N
2.
N
NH2
X = O, NH, S, CR2
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3.
Thiophene and thiazole more

bathochromic
VB theory sulphur atom plays a
decisive role by acting as an efficient
electron sink
PPP model cis-diene structure and
that the sulphur atom is not important

1. Tinctorial strength increases as the dyes become more

bathochromic with many exceptions
2. Directly related to the economic viability of a dye.
f = 4.703 x 10 x M x M
Eq. 3.1
f = 4.32 x 10-9 x 1/2 x max
Eq.3.2
29
Seoul National
(Dewars Rules)
(PPP Model)
Tinctorial Strength
Fig. 3.8. Relationship between

tinctorial strength and the area
under the absorption curve

In MO term, the transition dipole moment M must increase sufficiently
with increasing wavelength of absorption
X
O2N
N
N
NEt2
(126)
Direction of the transition

dipole moment lies along the
molecular from the donor D
the acceptor group A
The optimum orientation of
the molecule for maximum
absorption of radiation
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3.5.6 Protonated Azo Dyes

protonation of 4-aminobenzene
ammonium tautomer colorless
azonium tautomer colored
The Azonium Tautomer

azonium tautomer contains delocalized positive charge
more bathochromic, tinctorially stronger and brighter than neutral azo form
D
N
(127)
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NR2
H
N
N
N+R2
(127A)

1/2 of azonium tautomer is narrower than that of neutral azo form
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Table 3.17. Spectral effects in neutral and protonated azo dyes
Neutral Dye
EtOH
MeO
O2N
O2N
max (nm)
Azonium tautomer
EtOH/HCl
max (nm)
NMe2
408
516
NMe2
405, 440s
548
+32
NMe2
475
508
-8
NEt2
501
486
-30
MeO
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ring D of azonium tautomer
electron donating group bathochromic
electron withdrawing group hypsochromic

ring C of azonium tautomer
electron donating group hypsochromic
electron withdrawing group bathochromic

it is possible to obtain a dye in which the neutral and
protonated form exhibit the same colour
O2N
F3CO2S
Seoul National
EtOHmax 500 nm ;
N
max 29,800
NMe2
EtOH/HCl max 500 nm ; max 56,300

Table 3.18. Negative halochromism by substituents in ring D
X
NR2
Neutral Dye
EtOH
max (nm)
Me
Azonium form
EtOH/HCl
max (nm)
N N
596
506
-90
C C
CN
NC
592
586
-6
NC
Et
negative halochromism
- hypsochromic shift caused by protonation
- difficult to achieve by substitution of ring D
- achieved with electron-donating group meta to the terminal
amino group in ring C (table 3.16)
Seoul National

Azo dyes containing heterocyclic rings
also display negative halochromism
CO2Et
O 2N
NEt2
EtOH
max 594 nm ; 531 nm(EtOH/HCl)
Seoul National
O2N
NMe2
EtOH
max 554 nm ; 464 nm(EtOH/HCl)

First
excited
state
E e.w.
E e.d.
(132)
(132)
Fig. 3.10.
Effect of electron-withdrawing and
electron-donating groups on the
colour of azonium tautomers
Ground
state
(132)
X=Electron-donating
group
X=Electron-withdrawing
group
batochromicity
ground state of azonium tautomer (132) quinoid structure

first excited state of azonium tautomer (132A) benzenoid structure
electron donating group on ring D stabilize (132A),
but destabilize (132) which causes bathochromicity
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3.5.7 Azo-Hydrazone Tautomers

hydrazone tautomer
generally more batochromic than the azo tautomer
X
X
H
N
OH
(133A)
(134A)
Eazo
D
Ehyd.
N
(134)
Seoul National
OH
H
N
E
N
(133)

ring D of azo tautomer
- electron donating group hypsochromic
localize negative change of the first excited state (134A)
- electron withdrawing group bathochromic
ring D of hydrazone tautomer
- electron donating group bathochromic
reduce positive charge on hydrazo nitrogen atom (133A)
- electron withdrawing group hypsochromic
Table 3.19. Visible absorption maxima of the azo(134) and hydrazone (133) tautomers
para X
max (nm)
404
405
407
424
432
Seoul National
Hydrazone (133) in HOAc
Azo (134) in EtOH

MeOH
Me
H
CN
NO2
max (nm)
-3
-2
+17
+25
485
489
478
462
465
+7
+11
-16
-13

dyes in hydrazone tautomer:
electron-donating groups on D ring cause bathochromic shift
H O
D
H O
N
N
N
(136)
(135)
N
H
N
O
(137)
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R
N
N
Ar
R
D
N
H
N
O
R
N
R
(138)
3.5.8 Polyazo Dyes

non-conjugated polyazo dye
spectra is the sum of individual monoazo dyes
individual azo subunit is insulated by more than two single bonds
important insulationg groups
methylene
CH2
HNCONH
ureido
N
N
triazinyl
X
S
O
N
H
CO
Seoul National
3.5.8 Polyazo Dyes
Fig. 3.13.
The absorption spectra of an
insulated diazo dye and the
parent monoazo dye
Me2N
Me
CH2
NMe2
NMe2
disazo dye has similar colour, is 2 times stronger,

but has no economical advantage over the monoazo dye
Seoul National
3.5.8 Polyazo Dyes

linking of two different dyes:
produce tertiary shades but no economical advantage
O
HO3S
N
N
L
Cu
O
HO3S
O SO3H
NHCNH2
N
N
Cl
N
N
H
N
N
purple
SO3H
SO3H
N
H
brown
yellow
(143)
H
Ph N
N
N
H
N
N
OMe
NaO3S
NaO3S
HN
HO
N
N
Me
OH
blue
Seoul National
green
SO3Na N N
CO2Na
NaO3S
OH
(144)
yellow
3.5.8 Polyazo Dyes

A
N
N
N
N
increasing the electron-donating strength of the terminal group D

incorporation of electron-donating groups in M or E
changing M or E from phenyl to naphthyl
all cause a bathochromic shift
Seoul National
3.5.8 Polyazo Dyes

N
N
N
N
VB explanation
- bathochromic due to
stabilized first excited state
(146)
N
N
N
N
(147)
Seoul National
3.5.8 Polyazo Dyes

Y
hydrazo
imino
N
N
X
N
N
ortho C
HO3S
SO3H
para C
disazo dye
one of azo subunit exists in hydrazone form
three peaks (Fig. 3.14)
dull blues, greens or blacks
Seoul National
3.5.9 Steric Effects
steric hindrance in azo molecule

- cause hypsochromic or bathochromic shift
always lower tinctorial strength
3 types of steric hindrance in azo dyes
- at the azo group
at the dialkyl amino group of coupling ring
at the nitro group of diazo ring
Seoul National

Steric Hindrance at Azo Group
Two planar conformations are possible.
conformation (a) is sterically more crowded than conformation (b)
crowding between ortho substituent and electrons of nitrogen
N
N
(a)
N
N
(b)
Fig. 3.15. Alternative conformations for an ortho-substituted azobenzene
Seoul National

X
Z
N
N
Et
N
C2H4CN
(150)
Table 3.21. Absorption band of some derivatives of dye(150) in methanol

X
H
Cl
Cl
NO2
NO2
NO2
CN
H
CN
CN
max (nm)
H
H
Cl
H
H
NO2
H
H
H
CN
NO2
NO2
NO2
H
NO2
NO2
H
CN
NO2
NO2
453
475
417
425
491
520
434
433
504
549
Seoul National
max
44,000
40,000
31,000
36,000
38,000
48,000
42,000
45,000
45,000
38,000
+22
-36
-28
+38
+67
+51
+96

X
126
O2N
N 120
N
S
Ac
N
H
N(C2H4CO2Me)2
for 5-membered heterocyclic system used as diazo compounds

- steric hindrance between the ortho substituent and lone pair
orbital of the -azo nitrogen atom is diminished because of
larger bond angle
Seoul National

R1
O2N
N
N
NMe2
R
Table 3.22. Absorption bands of some ortho-substituted azo dyes
R1
R2
EtOH
(nm)
max
max
H
Me
Me
H
H
Me
480
495
468
30,400
31,000
26,800
+15
-12
one ortho substituent caused a bathochromic shift

two ortho substituents caused a hypsochromic shift
Seoul National

Steric Hindrance at the Terminal Dialkylamino Group
X
Z
N
N
NMe2
Y
Table 3.23 Absorption bands of some dyes with a sterically hindered terminal group
H
Me
Me
Cl
Me
Me
H
H
Me
H
H
Me
H
H
H
H
NO2
NO2
EtOH
max
(nm)
408
375
380
377
422
423
max
28,250
18,200
10,300
19,900
19,500
11,200
-33a
-28a
-31a
-57a
-56a
relative to (153 : X=Y=Z=H)
relative to (153: X=Y=H, Z=NO2)

Seoul National

Steric Hindrance at the Nitro Group
X
O2N
N
N
NMe2
(157)
Table 3.24 Absorption bands of dye
H
Me
Me
H
H
Me
Seoul National
max (nm)
479
460
443
max
31,300
32,000
31,000
-19
-36

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3.

5 Colour and Constitution

3.5 Colour and Constitution

3.5 Colour and Constitution

3.5 Colour and Constitution

3.5.2 Early Theories

3.5 Colour and Constitution

3.5.2 Early Theories

3.5 Colour and Constitution

3.5.2 Early Theories

Doebners violetTautomeric form

3.5 Colour and Constitution

3.5.3 Modern Theories

3.5 Colour and Constitution

3.5.3 Modern Theories

3.5 Colour and Constitution

3.5.3 Modern Theories

Excitation energy of ethylene vs. 1,3-butadiene

3.5 Colour and Constitution

3.5.4 Experimental Observations

the greater the electron donating power, the more bathochromic

3.5 Colour and Constitution

3.5.4 Experimental Observations

3.5 Colour and Constitution

3.5.4 Experimental Observations

Table 3.8. Combined effect of electron-donating and accepting

3.5.4 Experimental Observations

Table 3.9. Effect of electron-accepting groups in the coupling component ring C

3.5 Colour and Constitution

3.5.4 Experimental Observations

Effect of several electron

3.5 Colour and Constitution

3.5.4 Experimental Observations

Low because of steric hindrance(see 3.5.9).

3.5 Colour and Constitution

3.5.4 Experimental Observations

Typical violet dye

Typical blue dye

3.5 Colour and Constitution

3.5.4 Experimental Observations

3.5 Colour and Constitution

3.5.4 Experimental Observations

dyes with heterocycles as coupling components are more

3.5 Colour and Constitution

3.5.4 Experimental Observations

Data for Et compound is not available.

3.5 Colour and Constitution

3.5.5 Application of VB and MO Theories

Charge separated structure

3.5 Colour and Constitution

3.5.5 Application of VB and MO Theories

unfavourable situation with EDG at both sides

ortho- and para-cyano dyes

E is reduced and bathochromic shift

3.5 Colour and Constitution

3.5.5 Application of VB and MO Theories

No stabilisation of the excited state

substituents meta to the dialkylamino group (116A)

inductive and mesomeric (resonance) effect