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NH
NH
O
O
Cl
Cl
• Brilliant red or orange high performance pigmentsBrilliant red or orange high performance pigments• Extremely:Extremely: InsolubleInsoluble Resistant (Resistant (ΔΔT, hT, hνν,, etc.) etc.)• Used in:Used in: Luxury cars paintingLuxury cars painting High quality printingHigh quality printing Plastics coloringPlastics coloring Solar cells, OLED, Fluorescence imaging etc.Solar cells, OLED, Fluorescence imaging etc.
NH
NH
O
O
1974 – Farnum 1974 – Farnum et alet al – accidental discovery of DPP – accidental discovery of DPP11
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 patent1983 – Iqbal and Cassar patent22: : Synthesis of DPP by condensation of succinate with Synthesis of DPP by condensation of succinate with aromatic nitrilearomatic nitrile
RR11, , RR2 2 = = iiPr, Pr, ttBu, Bu, ttAm etc. Am 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
30-70 %
Reason: Reason: Strong molecular interactionsStrong molecular interactions3,43,4
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°
Reason: Reason: Strong molecular interactionsStrong molecular interactions3,43,4
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
Heat fastness: < 500°CHeat fastness: < 500°C 8th grade light resistance (1 to 8 scale)8th grade light resistance (1 to 8 scale) εε > 30000 M > 30000 M-1-1 · cm· cm-1-1
Low Stokes shift < 30 nm (< 0,75 eV) usually ~12-15 nmLow Stokes shift < 30 nm (< 0,75 eV) usually ~12-15 nm λλmaxmax: 500-550 nm: 500-550 nm Hypsochromic shift in solutionHypsochromic shift in solution Fluorescence quantum yield ~0,5Fluorescence quantum yield ~0,5 110 mg dissolves in 1L of DMF110 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
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 Ciba was selling this for $100 per kilo, and the cost was $20 per kilo, so it was a big advantage for the was $20 per kilo, so it was a big advantage for the company„company„ 66
‚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 Cl3
ArNH 2
bromination
acylation
Heating
Larger/More branched substituent = Better solubilityLarger/More branched substituent = Better solubility ΦΦFF increases up to 0,9increases up to 0,9 Stokes shift up to 70 nm (~2 eV)Stokes shift up to 70 nm (~2 eV) Lower temperature resistance (<300°C)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
Fluorescence imagingFluorescence imaging ElectroluminescenceElectroluminescence Solar cellsSolar cells Conductive polymersConductive polymers Photoconductive materialsPhotoconductive materials Two photon absorptionTwo photon absorption Ions and molecules fluorescent sernsorsIons and molecules fluorescent sernsors Laser dyesLaser dyes Optical data storageOptical data storage Liquid crystalsLiquid crystals Electrochromic materialsElectrochromic materials Field effect transistorsField effect transistors
8. High Performance Pigments, Faulkner E B, Schwartz R J, WILEY-VCH, Weinheim, 2009, p.191
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
CompoundCompound λλabsabs/nm/nm λλemem/nm/nm Δν/Δν/nmnm ΦΦ λλ22PAPA/nm/nm δδmaxmax/GM/GM δδmaxmax/MW/MW
DPP-RDPP-R 476476 546546 7070 0,670,67 730730 110110 0,310,31DPP-DPADPP-DPA 539539 604604 6565 0,370,37 810810 12001200 2,982,98DPP-TPADPP-TPA 508508 595595 8787 0,460,46 820820 930930 1,681,68
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
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 3
DM F
120 oC
NH
O
Pd(O Ac)2/SPhos
tBuO Na, PhM e
100 oC
2
2 2 + HCOOH 2 + TFA
11. Yamagata T, Kuwabara J, Kanbara T, Tetrahedron Lett., 2010, 51, 1596
0 – 10000 – 1000eq of TFAeq of TFA
1250 – 50001250 – 5000eq of TFAeq of TFA
22 in CHCl in CHCl33 (2 (2 · 10· 10-5-5 M) M)
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
CompoundCompound -Ar-Ar
11
22
33
Br
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
εε = 125 000 – 261 000 M = 125 000 – 261 000 M-1-1 cm cm-1-1
λλabsabs = 684 – 864 nm = 684 – 864 nmλλemem = 708 – 881 nm = 708 – 881 nmΦΦFF = 0,32 – 0,69 = 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, 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
17. Prashant S, Ging-Meng N, Ting Ting L, Ananth D, Zhi-Kuan C, J. Mater. Chem., 2010, 20, 3626
Electrochemical Electrochemical bangap: bangap: 1,63 – 1,74 eV1,63 – 1,74 eV
1% 1% power power conversion for conversion for TFPDPPTFPDPP