Diketopyrrolopyrroles
DPP
Cl
H
N
O
O
Marek Grzybowski
Cl
N
H
Introduction
• Brilliant red or orange high performance pigments
• Extremely:
H
 Insoluble
 Resistant (ΔT, hν, etc.)
• Used in:




O
N
N
H
O
Luxury cars painting
High quality printing
Plastics coloring
Solar cells, OLED, Fluorescence imaging etc.
History
1974 – Farnum et al – accidental discovery of DPP1
H
N
O
CN
Zn
+
O
O
H
N
Br
OEt
N
H
1. Farnum D G, Mehta G, Moore G G I, Siegal F P, Tetrahedron Lett. 1974, 15, 2549
O
5-20 %
N-Unsubstituted DPP - History
1983 – Iqbal and Cassar patent2:
Synthesis of DPP by condensation of succinate with
aromatic nitrile
CN
H
N
O
OR
+
OR
1
R2ONa, R2OH
1
T
O
R1 ,
R2 = iPr, tBu, tAm etc.
2. Iqbal A, Cassar L, Ciba-Geigy Ltd, US Patent 4, 1983, 415, 685
O
O
N
H
30-70 %
N-Unsubstituted DPP - Insolubility
Reason: Strong molecular interactions3,4
7°
1,82Å
3. Lenz R, Wallquist O, Surface Coatings International Part B: Coatings Transactions, 2002, 85, 1-xxx
4. Mizuguchi J, Grubenmann A, Wooden G, Rihs G, Acta Crystallographica, Section B, 1992, 48, 696
N-Unsubstituted DPP - Insolubility
Reason: Strong molecular interactions3,4
3,5Å
3,5Å
3. Lenz R, Wallquist O, Surface Coatings International Part B: Coatings Transactions, 2002, 85, 1-xxx
4. Mizuguchi J, Grubenmann A, Wooden G, Rihs G, Acta Crystallographica, Section B, 1992, 48, 696
N-Unsubstituted DPP – Properties








Heat fastness: < 500°C
8th grade light resistance (1 to 8 scale)
ε > 30000 M-1 · cm-1
Low Stokes shift < 30 nm (< 0,75 eV) usually ~12-15 nm
λmax: 500-550 nm
Hypsochromic shift in solution
Fluorescence quantum yield ~0,5
110 mg dissolves in 1L of DMF
Commercially available DPP pigments5
~ 2000 tonnes / year
-Ar =
Ferrari RedPigment
(Pigment
Red
254)
Red 255
Pigment Red 272
H
N
O
Cl
H
N
CH3
„Ciba was selling
O Ar this for $100 per kilo, and the cost
wasAr$20 per kilo, soPigment
it was
a big advantage
for the
Red 254
Pigment Red 264
6
N
company„
O
H
Cl
N
H
O
Cl
Pigment Orange 73
Pigment Orange 71
CN
5. Industrial Organic Pigments, Herbst W, Hunger K, WILEY-VCH, Weinheim, 2004, p.490
6. http://blog.cleveland.com/pdextra/2007/10/pollock_cuts.html
Modifications
R
O
N
S
O
N
‚Latent pigment’
RO
H
N
S
N
H
R
alkylation
O
Lawesson reagent
N
O
acylation
POCl3
OR
O
H
N
ArNH2
O
N
O
O
H
N
Heating
N
H
O
N
H
sulfonation
bromination
O
Br
Br
H
N
N
H
O
HO 3S
6. Zambounis J, Hao Z, Iqbal A, Nature, 1997, 388, 131
O
SO 3H
H
N
N
H
O
N
Ar
N-Alkylation
Insoluble becomes soluble
Ar
HN
O
NH
Ar
RX, DMF
K2CO3
R
N
O
N
R
120 oC
O




Ar
5-90 %7
O
Alcoxides and hydroxides
were also used as bases
Ar
Larger/More branched substituent = Better solubility
ΦF increases up to 0,9
Stokes shift up to 70 nm (~2 eV)
Lower temperature resistance (<300°C)
7. Colonna G, Pilati T, Rusconi F, Zecchi G, Dyes and Pigments, 2007, 75, 125
DPPs as Functional Dyes8












Fluorescence imaging
Electroluminescence
Solar cells
Conductive polymers
Photoconductive materials
Two photon absorption
Ions and molecules fluorescent sernsors
Laser dyes
Optical data storage
Liquid crystals
Electrochromic materials
Field effect transistors
8. High Performance Pigments, Faulkner E B, Schwartz R J, WILEY-VCH, Weinheim, 2009, p.191
Examples – Two photon absorption
Er Qian Guo et al9
9. Guo E Q, Ren P H, Zhang Y L, Zhang H C, Yang W J, Chem. Commun., 2009, 2859
Examples – Two photon absorption
Er Qian Guo et al9
Compound λabs/nm λem/nm Δν/nm
DPP-R
DPP-DPA
DPP-TPA
DPP-R
O
C8H17
546
604
595
Br
DPP-DPA
N
N
Br
476
539
508
O
O
70
65
87
Ph 2N
0,67
0,37
0,46
C8H17
λ2PA/nm δmax/GM δmax/MW
730
810
820
NPh 2
N
N
C8H17
Φ
O
C8H17
C8H17
DPP-TPA
O
N
NPh 2
Ph 2N
N
O
H17C8
9. Guo E Q, Ren P H, Zhang Y L, Zhang H C, Yang W J, Chem. Commun., 2009, 2859
110
1200
930
0,31
2,98
1,68
Examples – pH indicator
Takuya Yamagata et al11
Cl
Cl
H
N
O
N
O
O
BnBr, K2CO3
DMF
HN
NH
Bn
Pd(OAc)2/SPhos
tBuONa, PhMe
Bn
N
N
N
Bn
120 oC
O
O
O
100 oC
N
Bn
O
O
2
Cl
Cl
2
2 + HCOOH
11. Yamagata T, Kuwabara J, Kanbara T, Tetrahedron Lett., 2010, 51, 1596
2 + TFA
N
O
Examples – pH indicator
Takuya Yamagata et al11
0 – 1000
eq of TFA
2 in CHCl3 (2 · 10-5 M)
1250 – 5000
eq of TFA
11. Yamagata T, Kuwabara J, Kanbara T, Tetrahedron Lett., 2010, 51, 1596
Examples – F- chemosensor
Yi Qu et al12
C4H9
C4H9
O
O
N
N
Ar
Ar
FAr
Ar
N
H
N
O
O
H
F
Compound
1
-Ar
Br
2
3
12. Qu Y, Hua J, Tian H, Org. Lett., 2010, 12, 3320
Examples – NIR dyes
Georg M. Fisher et al13,14, 15, 16
POCl3
ε = 125 000 – 261 000 M-1 cm-1
λabs = 684 – 864 nm
λem = 708 – 881 nm
ΦF = 0,32 – 0,69
13. Fisher G M, Jüngst Ch, Isomäki-Krondahl M, Gauss D, Möller H M, Daltrozzo E, Zumbusch A, Chem. Comm., 2010, 46, 5289
14. Fischer G M, Ehlers A P, Zumbusch A, Daltrozzo E, Angew. Chem. Int. Ed., 2007, 46, 3750
15. Fischer G M, Daltrozzo E, Zumbusch A, Angew. Chem. Int. Ed., 2011, 50, 1406
16. Fischer G M, Isomäki-Krondahl M, Göttker-Schnetmann I, Daltrozzo E, Zumbusch A, Chem. Eur. J., 2009, 15, 4857
Examples – NIR dyes
Georg M. Fisher et al13,14, 15, 16
13. Fisher G M, Jüngst Ch, Isomäki-Krondahl M, Gauss D, Möller H M, Daltrozzo E, Zumbusch A, Chem. Comm., 2010, 46, 5289
14. Fischer G M, Ehlers A P, Zumbusch A, Daltrozzo E, Angew. Chem. Int. Ed., 2007, 46, 3750
15. Fischer G M, Daltrozzo E, Zumbusch A, Angew. Chem. Int. Ed., 2011, 50, 1406
16. Fischer G M, Isomäki-Krondahl M, Göttker-Schnetmann I, Daltrozzo E, Zumbusch A, Chem. Eur. J., 2009, 15, 4857
Examples – Solar cells
Prashant Sonar et al17
Electrochemical
bangap:
1,63 – 1,74 eV
1% power
conversion for
TFPDPP
17. Prashant S, Ging-Meng N, Ting Ting L, Ananth D, Zhi-Kuan C, J. Mater. Chem., 2010, 20, 3626
The End