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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

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Diketopyrrolopyrroles DPP

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  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, TetrahedronLett.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-GeigyLtd, US Patent 4, 1983, 415, 685

  5. N-Unsubstituted DPP - Insolubility Reason: Strongmolecular interactions3,4 7° 1,82Å 3. Lenz R, Wallquist O, SurfaceCoatings International Part B: CoatingsTransactions, 2002, 85, 1-xxx 4. Mizuguchi J, Grubenmann A, Wooden G, Rihs G, Acta Crystallographica, SectionB, 1992, 48, 696

  6. N-Unsubstituted DPP - Insolubility Reason: Strongmolecular interactions3,4 3,5Å 3,5Å 3. Lenz R, Wallquist O, SurfaceCoatings International Part B: CoatingsTransactions, 2002, 85, 1-xxx 4. Mizuguchi J, Grubenmann A, Wooden G, Rihs G, Acta Crystallographica, SectionB, 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. IndustrialOrganicPigments, 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 hydroxideswerealsoused 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, TetrahedronLett.,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, TetrahedronLett.,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, JüngstCh, 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, DaltrozzoE, ZumbuschA, Angew. Chem. Int. Ed., 2011, 50, 1406 16. Fischer G M, Isomäki-Krondahl M, Göttker-Schnetmann I,Daltrozzo E, ZumbuschA, Chem. Eur. J., 2009, 15, 4857

  18. Examples – NIR dyesGeorg M. Fisher et al13,14, 15, 16 13. Fisher G M, JüngstCh, 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, DaltrozzoE, ZumbuschA, Angew. Chem. Int. Ed., 2011, 50, 1406 16. Fischer G M, Isomäki-Krondahl M, Göttker-Schnetmann I,Daltrozzo E, ZumbuschA, 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, TingTing L, Ananth D, Zhi-Kuan C, J. Mater. Chem., 2010, 20, 3626

  20. The End

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