Diketopyrrolopyrroles DPP

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DiketopyrrolopyrrolesDPP
Marek Grzybowski
2
Introduction

• Brilliant red or orange high performance pigments
• Extremely
• Insoluble
• Resistant (?T, h?, etc.)
• Used in
• Luxury cars painting
• High quality printing
• Plastics coloring
• Solar cells, OLED, Fluorescence imaging etc.

3
History

• 1974 Farnum et al accidental discovery of
  DPP1

5-20
1. Farnum D G, Mehta G, Moore G G I, Siegal F P,
Tetrahedron Lett. 1974, 15, 2549
4
N-Unsubstituted DPP - History

• 1983 Iqbal and Cassar patent2
• Synthesis of DPP by condensation of succinate
  with aromatic nitrile
• R1, R2 iPr, tBu, tAm etc.

30-70
2. Iqbal A, Cassar L, Ciba-Geigy Ltd, US Patent
4, 1983, 415, 685
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N-Unsubstituted DPP - Insolubility

• Reason Strong molecular interactions3,4

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
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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
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N-Unsubstituted DPP Properties

• Heat fastness lt 500C
• 8th grade light resistance (1 to 8 scale)
• e gt 30000 M-1 cm-1
• Low Stokes shift lt 30 nm (lt 0,75 eV) usually
  12-15 nm
• ?max 500-550 nm
• Hypsochromic shift in solution
• Fluorescence quantum yield 0,5
• 110 mg dissolves in 1L of DMF

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Commercially available DPP pigments5 2000
tonnes / year
Ferrari Red (Pigment Red 254)
Ciba was selling this for 100 per kilo, and the
cost was 20 per kilo, so it was a big advantage
for the company 6
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
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Modifications
Latent pigment
6. Zambounis J, Hao Z, Iqbal A, Nature, 1997,
388, 131
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N-AlkylationInsoluble becomes soluble
Alcoxides and hydroxides were also used as bases
5-90 7

• Larger/More branched substituent Better
  solubility
• FF increases up to 0,9
• Stokes shift up to 70 nm (2 eV)
• Lower temperature resistance (lt300C)

7. Colonna G, Pilati T, Rusconi F, Zecchi G,
Dyes and Pigments, 2007, 75, 125
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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
12
Examples Two photon absorptionEr Qian Guo et
al9
9. Guo E Q, Ren P H, Zhang Y L, Zhang H C, Yang W
J, Chem. Commun., 2009, 2859
13
Examples Two photon absorptionEr Qian Guo et
al9
Compound ?abs/nm ?em/nm ??/nm F ?2PA/nm dmax/GM dmax/MW
DPP-R 476 546 70 0,67 730 110 0,31
DPP-DPA 539 604 65 0,37 810 1200 2,98
DPP-TPA 508 595 87 0,46 820 930 1,68
9. Guo E Q, Ren P H, Zhang Y L, Zhang H C, Yang W
J, Chem. Commun., 2009, 2859
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Examples Two photon absorptionJiangi Yihua et
al10
10. Jiang Y, Wang Y, Hua J, Qu S, Qian S, Tian H,
J. Polym. Sci. Part A Polymer Chemistry, 2009,
47, 4400
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Examples pH indicatorTakuya Yamagata et al11
2
2
2 HCOOH
2 TFA
11. Yamagata T, Kuwabara J, Kanbara T,
Tetrahedron Lett., 2010, 51, 1596
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Examples pH indicatorTakuya Yamagata et al11
2 in CHCl3 (2 10-5 M)
0 1000 eq of TFA
1250 5000 eq of TFA
11. Yamagata T, Kuwabara J, Kanbara T,
Tetrahedron Lett., 2010, 51, 1596
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Examples F- chemosensorYi Qu et al12
Compound -Ar
1
2
3
12. Qu Y, Hua J, Tian H, Org. Lett., 2010, 12,
3320
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Examples NIR dyesGeorg M. Fisher et al13,14,
15, 16
POCl3

• e 125 000 261 000 M-1 cm-1
• ?abs 684 864 nm
• ?em 708 881 nm
• FF 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
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Examples NIR dyesGeorg 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
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Examples Solar cellsPrashant 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
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The End?