18.11.04 ws 04/05-functional π-systems: part 2 1

» E. Breitmaier, G. Jung, Organische Chemie: Grundlagen,Stoffklassen, Reaktionen, Konzepte, Molekülstruktur, 4th ed.,Thieme, Stuttgart

» H. R. Christen, F. Vögtle, Organische Chemie - Von den Grundlagenzur Forschung, Vol. II, Vol. III, Otto Salle Verlag, Frankfurt

» H. Zollinger Colour Chemistry -Syntheses, Properties andApplications of Organic Dyes and Pigments, VCH, Weinheim

» L.-F. Tietze, T. Eicher, Reaktionen und Synthesen im organisch-chemischen Praktikum, Georg Thieme Verlag, Stuttgart

Part 2: Dyes and Pigments – Syntheses andProperties

18.11.04 ws 04/05-functional π-systems: part 2 2

N

SN

N NMe Me

MeX-

+blue colored

S

N

N

N H

2

N M e

2

+

2 H 2O 2/ F e

2 +

H C l

M e

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» S. Huenig, et. al., Angew. Chem. 1962, 74, 818-824.» L.-F. Tietze, T. Eicher, Reaktionen und Syntheses im organisch-chemischen

Praktikum, Georg Thieme Verlag, Stuttgart, 1981.

Synthesis of a blue colored azo dye

18.11.04 ws 04/05-functional π-systems: part 2 3

ØAstraphloxine FF∗ Sensitizer in photography» Christen, Vögtle, Organische Chemie, Vol II.

NH 3 C

N

C H 3

CH 3C H 3

CH 3 C H 3

+

X

-

λmax: ca 400 nm

N

MeMe

Me

Fischer-Base

startingmaterial

for the synthesis

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Cyanine dye

18.11.04 ws 04/05-functional π-systems: part 2 4

» P. F. Schatz, J. Chem. Ed. 2001, 78, 1442.

N

N

O

O

H

H

λmax: 621, 427 nm

N

O

H

starting material for the synthesis

indoxyl

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Indigo

18.11.04 ws 04/05-functional π-systems: part 2 5

OO

CO22 M+

red

O

OHHO

O

colorless

Ø synthesis from phthalic anhydride

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Phenolphthalein

18.11.04 ws 04/05-functional π-systems: part 2 6

» A. H. Schmidt, Synthesis 1980, 961-994.» R. West, Oxocarbons, Academic Press, New York,

1980.» S. Daehne, U. Resch-Genger, O. S. Wolfbeis, Near-

Infrared Dyes for High Technology Applications, Vol.52, Kluwer Academic Publishers, Dordrecht, 1998.

» H. Langhals, Angew. Chem. 2003, 115, 4422-4424.» M. Tian, S. Tatsuura, M. Furuki, I. Iwasa, L. S. Pu, J.

Am. Chem. Soc. 2003, 124, 348-349.

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Oxocarbons, oxocarbon dianions

18.11.04 ws 04/05-functional π-systems: part 2 7

∗ Dianions of a) squaric acid, b) croconic acid, c)rhodizonic acid

O

O

O

O

-

-

O

O

O

O

O

-

-

O

O

O

O

O

O

-

-

(CnOn)2-

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Oxocarbon dianions: Why are they so stable?

18.11.04 ws 04/05-functional π-systems: part 2 8

» H. E. Sprenger, W. Ziegenbein, Angew. Chem. Int. Ed. 1968, 7, 530.

O

O

NNMe

Me Me

Me

-

+

λmax: 630 nm in chloroformOO

OHHO

synthesisfrom

quadratic acid

Ø Application: high-density opticaldata discs, read out Ga/As diodelaser (800-830 nm)

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Bis(4-dimethylaminophenyl)squaraine

18.11.04 ws 04/05-functional π-systems: part 2 9

» J. Am. Chem.Soc. 2003, 125,348

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Synthesis of dyes with absorption maxima at 1.2 µµm

18.11.04 ws 04/05-functional π-systems: part 2 10

» J. Am. Chem. Soc.2003, 125, 348.

» Angew. Chem.2003, 115, 4422.

O OOO

N(C4H9)2(C4H9)2N O- +

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Formation of a NIR-dye with λλmax at 1.1 µµm

18.11.04 ws 04/05-functional π-systems: part 2 11

Tetraphenylporphin

N N

N NH

H

A B

CD

1

5

20 10

15

N

H

from

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Porphins/porphyrins

18.11.04 ws 04/05-functional π-systems: part 2 12

Copper phthalocyanine(blue)

N

N

N

N N

N

N

N

Cu(II)

O

O

O

from

from phthalic anhydride,urea, ammonium molybdate

(NH4)2MoO4

N

NH2

NH

isoindoleninetmf

» C. C. Leznoff, A. B. P. Lever, Phthalocyanines:Properties and Applications, 1989.

Phthalocyanines

18.11.04 ws 04/05-functional π-systems: part 2 13

Copper phthalocyanine(blue), λλmax ≈≈ 750 nm

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N

N

N

N N

N

N

N

Cu(II)

CN

CN

from

from phthalodinitrileCu/Cu(I)Cl, MoO3,in nitrobenzene,

NH3

» L.-F. Tietze, T. Eicher,Reaktionen und Synthesen imorganisch-chemischenPraktikum, Georg ThiemeVerlag, Stuttgart

Synthesis of a copper phthalocyanine

18.11.04 ws 04/05-functional π-systems: part 2 14

M. Kollmannsberger, PhD thesis, Universität Regensburg, 1999.

λmax: ca 500 nm

N Me

Me

H

from

2,4-Dimethylpyrrole B

NN

FF

X

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Bora-3a,4a-diaza-(s)-indacene

18.11.04 ws 04/05-functional π-systems: part 2 15

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O

CO2EtN CO2Et

EtO2C

N

NaNO2

Zn / HOAc

H3PO4

Synthesis of pyrrole (Knorr)

18.11.04 ws 04/05-functional π-systems: part 2 16

» M. Kollmannsberger, PhD thesis, Universität Regensburg, 1999.

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N CHO

NNBNN

FFBF3Et2O.

NN

+ TFA

CH2Cl2

DDQoderp-ChloranilN(iPr)2Et

Synthesis of Boradiazaindacenes

18.11.04 ws 04/05-functional π-systems: part 2 17

» Angew. Chem. Int. Ed. 2001, 40, 385-387.

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BNN

FF

NMe2

CHO

B NN

FF

Me2N

PipOAcToluol

∆∆+

λmax 600 nm

Synthesis of a NIR-absorbing Boradiazaindacene

18.11.04 ws 04/05-functional π-systems: part 2 18

» M. Kollmannsberger, PhD thesis, Universität Regensburg,1999.

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εε

0

8•104

λ λ (nm)

500300

fluorescenceabsorption

B

NN

FF

high quantum yield ofemission

Absorption and emission spectra

18.11.04 ws 04/05-functional π-systems: part 2 19

» J. Phys. Chem. A 1998, 102, 10211-10220.tmf

 

B

NN

FF

NMe2

hexane

acetonitrile

dioxane

Solvent dependent fluorescence

18.11.04 ws 04/05-functional π-systems: part 2 20

» Fresenius J. Anal. Chem. 1997, 359, 150-154. tmf

 

B

NN

FF

NMe2

H+

A pH-sensor based on a boradiazaindacene

18.11.04 ws 04/05-functional π-systems: part 2 21

ØDefinition∗ Light induced reversible change of color.∗ Reversible switching between two structural

forms at least one reaction pathway must bea photochemical one.

» J. Fritzsche, Comptes Rendus Acad. Sci., Paris 1867, 69, 1035.» Organic materials for optical data storage, B. L. Feringa, W. F.

Jager, B. d. Lange, Tetrahedron 1993, 49, 8267-8310.» Organic Photochromism, H. Bouas-Laurent, H. Duerr, Pure Appl.

Chem. 2001, 73, 639-665. tmf

Photochromism

18.11.04 ws 04/05-functional π-systems: part 2 22

» N. J. Turro, Modern Molecular Photochemistry, The Benjamin/CummingsPublishing Co., Menlo Park. tmf

Classification of photoreactions

18.11.04 ws 04/05-functional π-systems: part 2 23

SS N N

O

O

OH

XO

N

OO

NH

X

N

O

O

O

O

O

O SS

XO

dihydro-azulene

dihydro-benzene

ethenederivative quinone

spirooxazine 2H-pyran N-salicylidene-aniline

triphenylmethyl-derivative

dihydroindolizinexanthenone fulgide dihydrothieno-benzothiophene

azo

spiropyran

Basic structures of photochromic compounds

18.11.04 ws 04/05-functional π-systems: part 2 24

» J. Whittal, in Photochromism: Molecules and Systems (Eds.:H. Dürr, H. Bouas-Laurent), Elsevier, Amsterdam, 1990, 467-492. tmf

Fulgides: Photochromism

CH3CH3

O

O

O

OCH3

H3C

CH3

O

Me

H3C Me Me

O

O

OMe λλ344

λλ494

1

18.11.04 ws 04/05-functional π-systems: part 2 25

» J. Whittal, in Photochromism: Molecules and Systems (Eds.:H. Dürr, H. Bouas-Laurent), Elsevier, Amsterdam, 1990, 467-492. tmf

EtO2C CO2Et EtO2C CO2K

MeMeHO2C

MeMe

OMe

CO2H

MeMe

O

O

O

O

Me

Fulgides: Synthesis

18.11.04 ws 04/05-functional π-systems: part 2 26

» Chem. Commun. 1998, 2313-2314.

SS

Me

R RMe

SSR R

R = -CHO

λλmax = 317 nm

λλ310

λλmax = 580 nm

λλ580

A photochromic dithienylethene

18.11.04 ws 04/05-functional π-systems: part 2 27

» Chem. Commun. 1998, 2313-2314.tmf

S S ClSS

O O

Cl Cl

SS

Me

Cl ClMe

SS

Me

OCHMe

CHO

Synthesis of dithienylthiophenes

18.11.04 ws 04/05-functional π-systems: part 2 28

ØPhotochromism: Reversible switching between two structural formsat least one reaction pathway must be a photochemical one.

N

MeMe

Me

Fischer-Base

from

∗ 1,3,3-Trimethyl-2,3-dihydroindol-2-spiro-2‘-(6-nitro-2H-chromene) (colorless) onirradiation a blue compound is formed

» G. Berkovic, V. Krongauz, V. Weiss, Chem. Rev. 2000, 100, 1741-1753.

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Spiropyrans: Synthesis

ON

MeMe

Me

NO2

18.11.04 ws 04/05-functional π-systems: part 2 29

ØPhotochromism: Reversible switching between two structural formsat least one reaction pathway must be a photochemical one.

» G. Berkovic, V. Krongauz, V. Weiss, Chem. Rev. 2000, 100, 1741-1753.

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Spiropyran photochromism

ON

MeMe

Me

NO2∆∆

N

Me Me

Me

O

NO2

hνν (UV)

340 nm 600 nm

18.11.04 ws 04/05-functional π-systems: part 2 30

» Chem. Ber. 1986, 119, 2631-2646.

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CNH

CN

CN CN

DHA VHF

photochem

thermal

colorless colored

Ø electrocyclic reactions

Dihydroazulene Photochromism

18.11.04 ws 04/05-functional π-systems: part 2 31

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CNCN

CN

CN

NCCNphotonic

thermal

λλmax = 366 nm

λλmax = 480 nm

» Adv. Mater. 1990, 2, 366-369.

irradiation at 366 nm

complementary color

light absorbed

500 nm

Dihydroazulene - Vinylheptafulvene