Outline · 29.01.03 lcnf02k02aw.ppt - functional pi systems - k02 1 Outline ... Light-emitting...

29.01.03 lcnf02k02aw.ppt - functional pi systems - k02 1

��

Outline• Conjugated Hydrocarbons – Conducting Polymers• Strained Systems - Fullerenes• Heterocyclic Compounds• DNA Photolyase: Mechanism of light induced repair of thymine dimers• Organic Light Emitting Diode (Organische Leuchtdiode)

� H. S. Nalwa, ‘Handbook of Organic Conductive Molecules and Polymers, Volume 1and 2, Wiley, New York, 1997.

� A. Hirsch The Chemistry of the Fullerenes; Georg Thieme Verlag: Stuttgart, 1994.� H. Hopf Classics in Hydrocarbon Chemistry - Syntheses, Concepts, Perspectives;

Wiley-VCH, Weinheim, 2000.� A. F. Pozharskii, A. T. Soldatenkov, A. R. Katritzky, Heterocycles in Life and Society,

John Wiley, Chichester, 1997.� Elektrolumineszierende konjugierte Polymere - Polymere erstrahlen in neuem Licht:

A. Kraft, A. C. Grimsdale, A. B. Holmes, Angew. Chem. 1998, 110, 416-443.


about conducting polymers

pf


conductivity(S cm-1) of

organic andinorganicmaterials

pf

» A. G. MacDiarmid, Angew. Chem. 2001, 113, 2649-2659.


π-conjugated polymers: semiconducting andconducting materials

n

n

Polyacetylene (PA)» H. Shirakawa, Angew. Chem. , Int. Ed. 2001,

40, 2575.

Polyphenylene (PP)» A. J. Berresheim, M. Müller, and K. Müllen,

Chem. Rev., 1999, 99, 1747.

Hn

Polyphenylenevinylene (PPV)» A. Kraft, A. C. Grimsdale, and A. B. Holmes,

Angew. Chem., 1998, 110, 416.

pf


π-conjugated polymers: semiconducting and conductingmaterials

Polythiophene (PT)» J. Roncali, Chem. Rev. 1992, 92, 711-

738.

S n

Polyazulene (PAZ)» F. X. Redl, O. Koethe, K. Roeckl, W.

Bauer, J. Daub, Macromol. Chem.Phys. 2000, 201, 2091-2100.

n

Polyaniline (PANI)

» A. G. MacDiarmid, Angew.Chem. 2001, 113, 2649-2659.

N

H

N

H

N

H

NH

pf


electrically conducting materials: molecularinteraction and band structure

Electronic energy level:top: a dimer formed of twomonomers

bottom: large assembly ofisolated molecular units(atoms) - band structure

» A. J. Bard, 'Integrated ChemicalSystems - A Chemical Approach toNanotechnology', Wiley-Interscience,1994.

pf_lcnf


ring-opening-polymerisation

.pf

K. Knoll, R. R. Schrock, J. Am. Chem. Soc. 1989, 111, 7989-8004


synthesis of poly(p-phenylene) – Suzuki route

R

R

BrBr

R

R

* *n

R

R

B(OH)2Br

1. n-BuLi (1 mol)2. B(OCH3)3

3. HCl

Pd(OAc)2, PPh3

Na2CO3

» Coupling Method, see: A. Suzuki, Cross-coupling Reactions ofOrganoboron Compounds with Organic Halides. In Metal-catalyzed Cross-coupling reactions; Diederich, F.; Stang, P. J.Eds.; Wiley-VCH: Weinheim, 1998.

pf


synthesis of poly(p-phenylene) – Bergman rearrangement

R

* *n

R

RR

RR heat

n n

» Synthesis of Polyphenylene Derivatives by Thermolysis ofEndiynes and Dialkynylaromatic Monomers: J. A. John, J. M.Tour, Tetrahedron 1997, 53, 15515-15534.

pf


synthetic route to polyphenylenevinylene (PPV)

CH2

CH2

R

R

SS

CH3

CH3CH3

CH3

CH

R

R

CH2S

CH3 CH3 n

R

R

**n

Cl Cl Cl

+ +

+

NaOH

H2O

300°C

-(CH3)2S, HCl

pf

» Y. Geerts, G. Klärner, K. Müllen. Hydrocarbon Oligomers. InElectronic Materials: The Oligomer Approach; Muellen, K.; Wegner,G. Eds.; Wiley-VCH: Weinheim, 1998; pp. 1-103.


synthesis of polyphenylenevinylene (PPV)using metathesis reaction

» Synthetic method, see: M. Schuster, S. Blechert, Angew. Chem. 1997,109, 2125.

» K. Müllen, G. Wegner, ‘Electronic Materials: The Oligomer Approach’,Wiley-VCH, Weinheim, 1998 pf


cyclic voltammetry

» Cyclovoltammetrie - die "Spektroskopie" des Elektrochemikers: J. Heinze,Angew. Chem. 1984, 96, 823-840.

mp


cyclic voltammetry under diffusion controlled conditions(left) and surface-immobilized conditions such as a

conducting polymer film (right)

mp


azulene/polyazulene: electrochemical polymerisationand dotation

» A. Mirlach. Dissertation, Universität Regensburg 1993» A. Mirlach, M. Feuerer, J. Daub, Adv. Mater. 1993, 5, 450-453. pap

HH n

dotated polyazuleneconducting material

radical cation/polaron

+

n

anodicoxidation

dotationby

electrochemicaloxidation

azulenemonomer

polyazulenenonconducting material

insulator


azulene/polyazulene-cyclicvoltammetry

pap

Left side: CV of the initial process of electropolymerisationRight side: formation of a conducting film on the electrode

»A. Mirlach, M. Feuerer, J. Daub, Adv. Mater. 1993, 5, 450-453.»A. Mirlach. Dissertation, Universität Regensburg 1993


polyaniline – conducting and nonconducting Forms

» A. G. MacDiarmid, Angew. Chem. 2001, 113, 2649-2659. pf

N

H

N

H

N

H

NH

N

H

N

H

N N

N N N N

N

H

N

H

N

H

NH

++

completely reduced form(leucoemeraldine)

semioxidized form(emeraldine)

oxidized form(pernigraniline)

conducting statemade by oxidationof leucoemeraldineor protonation of

emeraldine


strained hydrocarbons

» H. Hopf Classics in Hydrocarbon Chemistry - Syntheses,Concepts, Perspectives; Wiley-VCH: Weinheim, 2000.

» A. Hirsch, Chemie in unserer Zeit 1994, 28, 79-87. pf

[1.1.1]-Propellane [2.2]-Paracyclophan

[5]-Helicene

BuckminsterfullereneC60

� Synthesis� Physical properties� Applications

lcnf


allotropic forms of carbon

diamond graphite fullerene

l / cnf


nanotubes

» Nanotubes: C. N. R. Rao, B. C. Satishkumar, A. Govindaraj, M. Nath,ChemPhysChem 2001, 2, 78-105.

» P. M. Ajayan, Chem. Rev. 1999, 99, 1787-1799. lcnf/sfg


cyclischetetrapyrrole

Phthalocyanin lcnf


chlorophyll und vitamin B12

lcnf


difluoroboradiaza-s-indacene

N NH

NH

N

N+

NB

FF

-

dipyrromethene isnonfluorescent

strongly fluorescent

BNN

FF

sbo/lcnf

absorption spectrum (left)emission spectrum (right)


photoinduced electron transfer in the excitedstate (PET-effect)

fluorescence isswitched „off“ due to

fast electron transfer inthe excited state

sbo/lcnf

NBN

N

F

F

Me

Me

acceptor-spacer-donor

*ET

donoracceptor excited state

S1

S1

BN

N

F

FN

Me

H

Me

acceptor

+

acceptor

electron transfer in theexcited state is inhibited,fluorescence turns „on“


conducting charge-transfersystems

pf/lcnf

» F. Wudl, Acc. Chem. Res. 1984, 17, 227-232., 99, 1787-1799.

» M. Pope, C. E. Swenberg ElectronicProcesses in Organic Crystals andPolymers, Second Edition; Oxford UnivPress: Oxford, UK, 1999.


gff_lcnf

��

∗ nomenclature of flavin: 7,8-dimethylbenzo[g]pteridine-2,4(3H,10H)-dione

∗ Riboflavin, Vitamin B2

∗ FMN: riboflavin-5‘-phosphate (D-ribityl unit)∗ major absorption bands of flavin in its oxidized form:

(1)446, (2)375, (3)265, 220 nm (polarization according tothe right side formula)


gff_lcnf

�� !��

∗ !��"��#∗ !��!��!��$%�"��#&��'��&Φ��()�*&��+�,

∗ �%��%��!��!��- λ�.�*/(� &�0�/1(2&��$�3��&�Φ�

()((/�4

�)��)�+��&��%� )��!)�5��)��&�//&�/13678�)��)�+��)��%��%��!%� ��"��)�9��%� ��"��:��!%� ��"��;" ��8��<��&��)��)8��5��:�!��5��&��8�=��)�/8��)�/,/3/76)

��!��!�


reaction at C(8)-methyl gpe_lcnf

� P. J. Bruice, Organic Chemistry, Prentice-Hall

• flavin covalently attached to apoprotein: Cysteinyl-8α-FAD(monoamine oxidase, catalyzes the reaction of primary amin toaldehyde)


flavin chemistry: enzymatic processes gpe_lcnf



FAD-dehydrogenase:Oxidation of a dithiol

gpe_lcnf

SH SH

O

OS S

O

O+ FAD

dihydrolipoyldehydrogenase + FADH2

N N O

NN

O

R

H

Me

Me

H+

S RS

H+


SS

R

>+


gff_lcnf

��!��

��)��$��& �� &��?�5�$��$&��

N

NN

N

O

O

H

R

N

N

C

N

NH

O

O

H

R

N

NN

N

O

O

H

R

H

H

N

NN+

N

O

O

H

R H

N

NN

N

O

O

R

N

NN

N+

O

O

H

R

H

H

N

NN

N

O

O

H

R

N

NN

N+

O

O

H

R

H

H

H

N

NN

N

O

O

H

R

H

e+

e -

pK = 0

pK = 10-

-

e+

e --

-

pK = 2.3

pK = 8.3

pK < 0

pK = 6.7

e+

e --

-

e+

e --

-

FloxH2+

FloxH

Flox-

FlradH3+

FlradH2

FlradH-

FlredH4+

FlredH3

FlredH2-

��

��!��@��!��@�A��


ribbon diagram of DNAphotolyase of Eschericia coli

gnl_lcnf

Science 1995, 268,1866-1872.

α/β domain: whiteMTHF: light grayhelical domain: goldFAD: greenAMP: red


$��B�!��

�%��"��

� �!��!��&��CD&�,*(3,*1)� ��)�E)��$)��%� )��&/�D13/�1C)

antenna

excitation energy transfer

��!��F��$��!��


��B�!��

��$��!��$%�� $��!��

� Organic electroluminescent diodes: C. W. Tang, S. A. VanSlyke, Appl. Phys.Lett. 1987, 51, 913-915.

� Light-emitting diodes based on conjugated polymers: J. H. Burroughes, D. D.C. Bradley, A. R. Brown, R. N. Marks, K. MacKay, R. H. Friend, P. L. Burn, A.B. Holmes, Nature 1990, 347, 539-541.

� Efficient Two Layer LEDs on a Polymer Blend Basis: J. Pommerehne, H.Vestweber, W. Guss, R. F. Mahrt, H. Bässler, M. Porsch, J. Daub, Adv.Mater. 1995, 7, 551-554.

� Electroluminescence with Organic Compounds: J. Salbeck, Ber. Bunsenges.Phys. Chem. 1996, 100, 1667-1677.

� Elektrolumineszierende konjugierte Polymere - Polymere erstrahlen inneuem Licht: A. Kraft, A. C. Grimsdale, A. B. Holmes, Angew. Chem. 1998,110, 416-443.

� The electroluminescence of organic materials: U. Mitschke, P. Baeuerle, J.Mater. Chem. 2000, 10, 1471-1507.


��B�!��

��$��!��$%�� $��- 4��!��!��

� Angew. Chem. 1998, 110,416-443)

a: photoluminescence

b: electroluminescence


��B�!��

��$��!��$%�� $��- 4��" ��

� ��)��%"�)��)��&1/&�7/6

� ��&��&11/311D)

� � ��&��&�/**,3/*,,)

Polymer- LED‘s use polymers suchas PPV as electroluminescentmaterials: Nature 1990, 347, 539-541.


��B�!��

��$��!��$%�� $��- 4��" ��3

� Nature 1990, 347, 539-541; Angew. Chem. 1998, 110, 416-443)

Date post:	21-Aug-2018
Category:	Documents
Upload:	vudat
View:	221 times
Download:	0 times

Outline · 29.01.03 lcnf02k02aw.ppt - functional pi systems - k02 1 Outline ... Light-emitting...

Documents