Diketopyrrolopyrroles DPP
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Diketopyrrolopyrrol es DPP Marek Grzybowski N H N H O O Cl Cl
description
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 - PowerPoint PPT Presentation
Transcript of Diketopyrrolopyrroles DPP
DiketopyrrolopyrrolesDPP
Marek Grzybowski NH
NH
O
O
Cl
Cl
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.
NH
NH
O
O
History
1974 – Farnum et al – accidental discovery of DPP1
NH
NH
O
O
CN+
BrOEt
O
NH
O
Zn
1. Farnum D G, Mehta G, Moore G G I, Siegal F P, Tetrahedron Lett. 1974, 15, 2549
5-20 %
1983 – Iqbal and Cassar patent2: Synthesis of DPP by condensation of succinate with aromatic nitrile
R1, R2 = iPr, tBu, tAm etc.
CN
+OR
1
OR1
O
ONH
NH
O
OR 2O Na, R 2O H
T
2. Iqbal A, Cassar L, Ciba-Geigy Ltd, US Patent 4, 1983, 415, 685
N-Unsubstituted DPP - History
30-70 %
Reason: Strong molecular interactions3,4
3. Lenz R, Wallquist O, Surface Coatings International Part B: Coatings Transactions, 2002, 85, 1-xxx4. Mizuguchi J, Grubenmann A, Wooden G, Rihs G, Acta Crystallographica, Section B, 1992, 48, 696
1,82Å
7°
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-xxx4. Mizuguchi J, Grubenmann A, Wooden G, Rihs G, Acta Crystallographica, Section B, 1992, 48, 696
N-Unsubstituted DPP - Insolubility
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
NH
NH
Ar
O
O
Ar
CN
Cl
CH3
-Ar =
Pigment Orange 71Pigment Orange 73
Pigment Red 254 Pigment Red 264
Pigment Red 272Pigment Red 255
NH
NH
O
O
Cl
Cl
Ferrari Red (Pigment Red 254)
Commercially available DPP pigments5
~ 2000 tonnes / year
5. Industrial Organic Pigments, Herbst W, Hunger K, WILEY-VCH, Weinheim, 2004, p.4906. http://blog.cleveland.com/pdextra/2007/10/pollock_cuts.html
„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
Modifications
‚Latent pigment’
6. Zambounis J, Hao Z, Iqbal A, Nature, 1997, 388, 131
NH
NH
O
O
NH
NH
N
O
Ar
NH
NH
O
O
Br
Br
N
N
O
O
ORO
O OR
NH
NH
S
S
N
N
O
O
R
R
NH
NH
O
O
SO3H
HO3S
alkylationLawesson reagent
sulfonation
PO C l3
ArNH 2
bromination
acylation
Heating
N-AlkylationInsoluble becomes soluble
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)
NN
Ar
Ar O
O
R RNHNH
Ar
Ar O
O
RX, DM FK 2CO 3
120 oC
7. Colonna G, Pilati T, Rusconi F, Zecchi G, Dyes and Pigments, 2007, 75, 125
Alcoxides and hydroxides were also used as bases
5-90 %7
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 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
9. Guo E Q, Ren P H, Zhang Y L, Zhang H C, Yang W J, Chem. Commun., 2009, 2859
Compound λabs/nm λem/nm Δν/nm Φ λ2PA/nm δmax/GM δmax/MW
DPP-R 476 546 70 0,67 730 110 0,31DPP-DPA 539 604 65 0,37 810 1200 2,98DPP-TPA 508 595 87 0,46 820 930 1,68
N
N
O
O
Br
Br
C8H17
C8H17
DPP-R
N
N
O
O
C8H17
C8H17
NPh2
Ph2N
DPP-DPA
N
N
O
OC8H17
H17C8
NPh2
Ph2N
DPP-TPA
Examples – Two photon absorptionEr Qian Guo et al9
Examples – pH indicatorTakuya Yamagata et al11
11. Yamagata T, Kuwabara J, Kanbara T, Tetrahedron Lett., 2010, 51, 1596
NHNH
O
O
Cl
Cl
NN
O
O
Cl
Cl
Bn Bn
N
N
O
OBn
Bn
N
O
N
O
BnBr, K 2CO 3DM F
120 oC
NH
OPd(O Ac)2/SPhostBuO Na, PhM e
100 oC
2
2 2 + HCOOH 2 + TFA
Examples – pH indicatorTakuya Yamagata et al11
11. Yamagata T, Kuwabara J, Kanbara T, Tetrahedron Lett., 2010, 51, 1596
0 – 1000eq of TFA
1250 – 5000eq of TFA
2 in CHCl3 (2 · 10-5 M)
Examples – F- chemosensorYi Qu et al12
12. Qu Y, Hua J, Tian H, Org. Lett., 2010, 12, 3320
N
NH
O
O
C4H9
Ar
Ar
F -
N
N
O
O
C4H9
Ar
Ar
F
H
Compound -Ar
1
2
3
Br
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, 528914. Fischer G M, Ehlers A P, Zumbusch A, Daltrozzo E, Angew. Chem. Int. Ed., 2007, 46, 375015. Fischer G M, Daltrozzo E, Zumbusch A, Angew. Chem. Int. Ed., 2011, 50, 140616. Fischer G M, Isomäki-Krondahl M, Göttker-Schnetmann I, Daltrozzo E, Zumbusch A, Chem. Eur. J., 2009, 15, 4857
POCl3
ε = 125 000 – 261 000 M-1 cm-1
λabs = 684 – 864 nmλem = 708 – 881 nmΦF = 0,32 – 0,69
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, 528914. Fischer G M, Ehlers A P, Zumbusch A, Daltrozzo E, Angew. Chem. Int. Ed., 2007, 46, 375015. Fischer G M, Daltrozzo E, Zumbusch A, Angew. Chem. Int. Ed., 2011, 50, 140616. Fischer G M, Isomäki-Krondahl M, Göttker-Schnetmann I, Daltrozzo E, Zumbusch A, Chem. Eur. J., 2009, 15, 4857
Examples – Solar cellsPrashant Sonar et al17
17. Prashant S, Ging-Meng N, Ting Ting L, Ananth D, Zhi-Kuan C, J. Mater. Chem., 2010, 20, 3626
Electrochemical bangap: 1,63 – 1,74 eV
1% power conversion for TFPDPP
The End
