1 / 20

Diketopyrrolopyrroles DPP

Diketopyrrolopyrroles DPP. Marek Grzybowski. Introduction. Brilliant red or orange high performance pigments Extremely : Insoluble Resistant ( Δ T, h ν , etc.) Used in: Luxury cars painting High quality printing Plastics coloring

zorina
Download Presentation

Diketopyrrolopyrroles DPP

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. DiketopyrrolopyrrolesDPP Marek Grzybowski

  2. Introduction • Brilliant red ororange high performance pigments • Extremely: • Insoluble • Resistant (ΔT, hν, etc.) • Used in: • Luxurycars painting • High quality printing • Plastics coloring • Solar cells, OLED, Fluorescenceimaging etc.

  3. History 1974 – Farnumet al – accidentaldiscovery of DPP1 5-20 % 1. Farnum D G, Mehta G, Moore G G I, Siegal F P, Tetrahedron Lett.1974, 15, 2549

  4. N-UnsubstitutedDPP- History 1983 – Iqbal and Cassar patent2: Synthesis of DPP by condensation of succinate with aromaticnitrile 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: Strongmolecular 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

  6. N-Unsubstituted DPP - Insolubility Reason: Strongmolecular 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-UnsubstitutedDPP – Properties • Heatfastness: < 500°C • 8th gradelightresistance (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 • Hypsochromicshift in solution • Fluorescence quantum yield ~0,5 • 110 mg dissolves in 1L of DMF

  8. Commerciallyavailable 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

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

  10. N-AlkylationInsolublebecomessoluble • Larger/Morebranchedsubstituent = Bettersolubility • ΦFincreasesup to 0,9 • Stokes shiftup to 70 nm (~2 eV) • Lower temperatureresistance (<300°C) Alcoxides and hydroxides were also used as bases 5-90 %7 7. Colonna G, Pilati T, Rusconi F, Zecchi G, Dyes and Pigments, 2007, 75, 125

  11. DPPs as Functional Dyes8 • Fluorescenceimaging • Electroluminescence • Solar cells • Conductivepolymers • Photoconductive materials • Twophotonabsorption • Ionsand moleculesfluorescentsernsors • Laser dyes • Optical data storage • Liquid crystals • Electrochromic materials • Field effecttransistors 8. High Performance Pigments, Faulkner E B, Schwartz R J, WILEY-VCH, Weinheim, 2009, p.191

  12. Examples – TwophotonabsorptionEr QianGuoet al9 9. Guo E Q, Ren P H, Zhang Y L, Zhang H C, Yang W J, Chem. Commun.,2009, 2859

  13. Examples – TwophotonabsorptionEr QianGuoet al9 9. Guo E Q, Ren P H, Zhang Y L, Zhang H C, Yang W J, Chem. Commun.,2009, 2859

  14. Examples – pHindicatorTakuyaYamagataet al11 2 2 2 + HCOOH 2 + TFA 11. Yamagata T, Kuwabara J, Kanbara T, Tetrahedron Lett.,2010, 51, 1596

  15. Examples – pHindicatorTakuyaYamagataet al11 2 in CHCl3 (2 · 10-5M) 0 – 1000 eq of TFA 1250 – 5000 eq of TFA 11. Yamagata T, Kuwabara J, Kanbara T, Tetrahedron Lett.,2010, 51, 1596

  16. Examples – F-chemosensorYiQuet al12 12. Qu Y, Hua J, Tian H, Org. Lett., 2010, 12, 3320

  17. Examples – NIR dyesGeorg 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

  18. 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

  19. Examples – Solar cellsPrashant Sonar et al17 Electrochemicalbangap: 1,63 – 1,74 eV 1% powerconversion for TFPDPP 17. Prashant S, Ging-Meng N, Ting Ting L, Ananth D, Zhi-Kuan C, J. Mater. Chem., 2010, 20, 3626

  20. The End

More Related