Brilliant red or orange high performance pigments Brilliant red or orange high performance pigments...

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N H N H O O Cl Cl

Transcript of Brilliant red or orange high performance pigments Brilliant red or orange high performance pigments...

Page 1: Brilliant red or orange high performance pigments Brilliant red or orange high performance pigments Extremely: Extremely: Insoluble Insoluble Resistant.

NH

NH

O

O

Cl

Cl

Page 2: Brilliant red or orange high performance pigments Brilliant red or orange high performance pigments Extremely: Extremely: Insoluble Insoluble Resistant.

• 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

Page 3: Brilliant red or orange high performance pigments Brilliant red or orange high performance pigments Extremely: Extremely: Insoluble Insoluble Resistant.

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 %

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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 %

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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

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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

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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

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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

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‚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

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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

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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

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9. Guo E Q, Ren P H, Zhang Y L, Zhang H C, Yang W J, Chem. Commun., 2009, 2859

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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

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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

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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)

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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

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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

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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

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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

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