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Diketopyrrolopyrroles DPP

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Presentation on theme: "Diketopyrrolopyrroles DPP"— Presentation transcript:

1 Diketopyrrolopyrroles DPP
Marek Grzybowski

2 Introduction Brilliant red or orange high performance pigments
Extremely: Insoluble Resistant (ΔT, hν, etc.) Used in: Luxury cars painting High quality printing Plastics coloring Solar cells, OLED, Fluorescence imaging etc.

3 History 5-20 % 1974 – Farnum et al – accidental discovery of DPP1
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

5 N-Unsubstituted DPP - Insolubility
Reason: Strong molecular interactions3,4 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

6 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

7 N-Unsubstituted DPP – Properties
Heat fastness: < 500°C 8th grade light resistance (1 to 8 scale) ε > M-1 · cm-1 Low Stokes shift < 30 nm (< 0,75 eV) usually ~12-15 nm λmax: nm Hypsochromic shift in solution Fluorescence quantum yield ~0,5 110 mg dissolves in 1L of DMF

8 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.

9 Modifications ‚Latent pigment’
6. Zambounis J, Hao Z, Iqbal A, Nature, 1997, 388, 131

10 N-Alkylation Insoluble becomes soluble
Alcoxides and hydroxides were also used as bases 5-90 %7 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

11 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 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

13 Examples – Two photon absorption Er Qian Guo et al9
Compound λabs/nm λem/nm Δν/nm Φ λ2PA/nm δmax/GM δmax/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

14 Examples – Two photon absorption Jiangi 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

15 Examples – pH indicator Takuya Yamagata et al11
2 2 2 + HCOOH 2 + TFA 11. Yamagata T, Kuwabara J, Kanbara T, Tetrahedron Lett., 2010, 51, 1596

16 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

17 Examples – F- chemosensor Yi Qu et al12
Compound -Ar 1 2 3 12. Qu Y, Hua J, Tian H, Org. Lett., 2010, 12, 3320

18 Examples – NIR dyes Georg M. Fisher et al13,14, 15, 16
POCl3 ε = – 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

19 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

20 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

21 The End


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