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01.02.05 ws 04/05-functional π-systems: part 3 1
Outline
Ø Introduction
Ø Organic conducting molecules and polymers
Ø Fullerenes and nanotubes
Ø Flavins, DNA Photolyase
Ø Organic Light Emitting Diodes (OLED)
Part 3: Functional ππ-systems
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01.02.05 ws 04/05-functional π-systems: part 3 2
» J. Olmsted, III, G. M. Williams, Chemistry, 3rd ed., JohnWiley & Sons, New York, 2002.
» J.-M. Lehn, Supramolecular Chemistry Concepts andPerspectives, VCH, Weinheim, 1995.
» Der Weg zu einer neuen Materialklasse: Elektrischleitfähige Kunststoffe: M. Rehahn, Chemie in unserer Zeit2003, 37, 18-30.
» A. Hirsch The Chemistry of the Fullerenes; Thieme,Stuttgart, 1994.
» Elektrolumineszierende konjugierte Polymere - Polymereerstrahlen in neuem Licht: A. Kraft, A. C. Grimsdale, A.B. Holmes, Angew. Chem. 1998, 110, 416-443.
Books and articles
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01.02.05 ws 04/05-functional π-systems: part 3 3
The scaling of matter
» A. J. Bard, Integrated Chemical Systems - AChemical Approach to Nanotechnology, Wiley-Interscience, New York, 1994.
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01.02.05 ws 04/05-functional π-systems: part 3 4
Functional molecular and supramolecular devices
» J.-M. Lehn, Supramolecular Chemistry Concepts andPerspectives, VCH, Weinheim, 1995.
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01.02.05 ws 04/05-functional π-systems: part 3 5
Conductivity of organic and inorganic materials
» A. G. MacDiarmid, Angew.Chem. 2001, 113, 2649.
σσ= n⋅⋅e⋅µ⋅µ [S•cm-1] σσ: conductivity
µ: mobilitye: electron charge
n: number of chargecarriers
σσ
conductivity
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01.02.05 ws 04/05-functional π-systems: part 3 6
Band structure of lithium clusters Lin
J. Olmsted, III, G. M. Williams, Chemistry, 3rd
ed., John Wiley & Sons, New York, 2002.
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01.02.05 ws 04/05-functional π-systems: part 3 7
pf
From a semiconductor to a conductor
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01.02.05 ws 04/05-functional π-systems: part 3 8
Energetic diagram showing dotation
valence band
conducting band
» Angew. Chem. 2001, 113, 2660-2682.
Ø hole polaron (model owes to thedeformation of the lattice ondotation)
Ø singly occupied mid-band state
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01.02.05 ws 04/05-functional π-systems: part 3 9
Interesting articles to read
» "Organic metals" - the intermolecular migration ofaromaticity, J. H. Perlstein, Angew. Chem. 1977,89, 534-549.
» Polarons, bipolarons, and solitons in conductingpolymers, J. L. Brédas, G. B. Street, Acc. Chem.Res. 1985, 18, 309-315.
» Der Weg zu einer neuen Materialklasse: Elektrischleitfähige Kunststoffe, M. Rehahn, Chemie inunserer Zeit 2003, 37, 18-30.
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01.02.05 ws 04/05-functional π-systems: part 3 10
The charge-transfer effect and conductivity
pf/lcnf
CN
CNNC
NCS
S S
S S
S S
SS
S S
S
Tetracyanoquino-dimethane
(TCNQ)electron acceptor
Tetrathiafulvalene(TTF)
electron donor
BEDT-TTF
Ø BEDT-TTF: Bis(ethylenedithio)tetrathiafulvalene, beyond 4 Ksuperconductive on doping: (BEDT-TTF)2Cu(CF3)4 (J. Chem.Soc., Chem. Comm. 1994, 1599)
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01.02.05 ws 04/05-functional π-systems: part 3 11
Synthesis of tetrathiafulvalene
pf/lcnf
EtO2C CO2EtS
SS
S
S S
S
(TTF)+
first step
Ø An Improved Synthesis of Tetrathiafulvalene, L. R.Melby, H. D. Hartzler, W. A. Sheppard, J. Org. Chem.1974, 36, 2456-2458.
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01.02.05 ws 04/05-functional π-systems: part 3 12
Synthesis of tetracyanoquinodimethane
pf/lcnf
O
O
NC
NC
CN
CN
CH2(CN)2
TiCl4pyridineCH2Cl2
r.t.24 h
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01.02.05 ws 04/05-functional π-systems: part 3 13
A conducting material
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.
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01.02.05 ws 04/05-functional π-systems: part 3 14
Ø Elektrisch leitfähige Materialien: Elektrisch leitende
Polymere
Ø Bandstruktur
Ø Verbindungsklassen - Synthese
Ø Leitfähigkeit - Dotierung: Vom Halbleiter zum Leiter
Ø Fullerene - Nanotubes
Vorlesung: 21. 01. 2005
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01.02.05 ws 04/05-functional π-systems: part 3 15
About conducting polymers
pf
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01.02.05 ws 04/05-functional π-systems: part 3 16
pf
Linear combination of atomic orbitals (p-orbitals):From atomic orbitals to the band structure
» Der Weg zu einer neuen Materialklasse: Elektrisch leitfähigeKunststoffe, M. Rehahn, Chemie in unserer Zeit 2003, 37, 18.
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01.02.05 ws 04/05-functional π-systems: part 3 17
ππ-Conjugated polymers: semiconducting materials - 1
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
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01.02.05 ws 04/05-functional π-systems: part 3 18
ππ-Conjugated polymers: semiconducting materials - 2
Polythiophene (PT)» J. Roncali, Chem. Rev. 1992, 92, 711-
738.
Sn
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
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01.02.05 ws 04/05-functional π-systems: part 3 19
Metathesis based ring-opening-polymerisation
. » Acc. Chem. Res. 1990, 23, 158-165.
CF3CF3CF3CF3
R1
R2
R3
R1
R2
R3
R2
R1R3
CF3CF3
cat
n n
∆∆
cat: (RO-)2W(=N-Ar)(=CHR)
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01.02.05 ws 04/05-functional π-systems: part 3 20
Ring-opening-polymerisation - References
.pf
» Olefin metathesis and beyond, A. Fürstner, Angew. Chem. Int. Ed.2000, 39, 3012-3043.
» K. J. Ivin, J. C. Mol, Olefin Metathesis and Metathesis Polymerization,Academic Press, San Diego, 2003.
» Die Olefinmetathese - neue Katalysatoren vergrößern dasAnwendungspotential, M. Schuster, S. Blechert, Chemie in unsererZeit 2001, 35, 24-29.
» Living ring-opening metathesis polymerization catalyzed by well-characterized transition-metal alkylidene complexes, R. R. Schrock,Acc. Chem. Res. 1990, 23, 158-165.
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01.02.05 ws 04/05-functional π-systems: part 3 21
Suzuki reaction - mechanism
1: oxidative addition2: transmetalation3: reductive elimination
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01.02.05 ws 04/05-functional π-systems: part 3 22
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 of OrganoboronCompounds with Organic Halides. In Metal-catalyzed Cross-coupling reactions;Diederich, F.; Stang, P. J. Eds.; Wiley-VCH: Weinheim, 1998.
pf
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01.02.05 ws 04/05-functional π-systems: part 3 23
Poly(p-phenylene) – Bergman cyclization
R
* *n
R
RR
RR heat
n n
» Tetrahedron 1997, 53, 15515-15534.pf
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01.02.05 ws 04/05-functional π-systems: part 3 24
Calicheamicin - Bergman cyclization in Nature
» Angew. Chem. 1991, 103, 1453-1481.
tbb
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01.02.05 ws 04/05-functional π-systems: part 3 25
Calicheamicin - biological function
tbb
» Angew. Chem. 1991,103, 1453-1481.
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01.02.05 ws 04/05-functional π-systems: part 3 26
Methodology of PPV synthesis
pf
∗ Dehydrohalogenation∗ Elimination of sulfonium salts∗ Knoevenagel condensation∗ Horner condensation∗ Wittig condensation∗ Heck reaction∗ Suzuki reaction
R
R
**n
Polyvinylenephenylene(PPV)
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01.02.05 ws 04/05-functional π-systems: part 3 27
Synthetic route towards 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
» Electronic Materials: The Oligomer Approach; Muellen, K.; Wegner,G. Eds.; Wiley-VCH: Weinheim, 1998; 1.
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01.02.05 ws 04/05-functional π-systems: part 3 28
Synthesis of PPV: Metathesis reaction
» Bull. Chem. Soc. Jpn. 1992, 65, 853-857
MMA
Ø Acyclic diene metathesis (ADMET): only oligo(phenylenevinylene)sare formed
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01.02.05 ws 04/05-functional π-systems: part 3 29
Cyclic voltammetry
» Angew. Chem. 1984, 96, 823-840.mp
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01.02.05 ws 04/05-functional π-systems: part 3 30
mp
Cyclic voltammetry (CV)
diffusion controlledconditions
conductingpolymer film
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01.02.05 ws 04/05-functional π-systems: part 3 31
Ø Elektrische Leitfähigkeit: Dotierung
Ø Elektrisch leitende Polymere
- Polyazulen
- Polyanilin
Ø Fullerene
- Struktur
- Funktionalisierung und Einschlussverbindungen
Ø Nanotubes
Vorlesung: 28. 01. 2005
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01.02.05 ws 04/05-functional π-systems: part 3 32
Polyazulene
n
oxidation
azulene polyazulene
non-conducting form(isolator)
conducting form(semiconductor)
oxidation
"radical cations"
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01.02.05 ws 04/05-functional π-systems: part 3 33
Cyclic voltammetry (CV) of film formation of polyazulene
Ø Adv. Mater. 1993, 5, 450-453.
CV of monomer (irreversible)
CV of polymeric film
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01.02.05 ws 04/05-functional π-systems: part 3 34
Polyaniline – general formula
» A. G. MacDiarmid, Angew. Chem. 2001, 113, 2649-2659. pf
N
H
N
H
N N
X
( ) ( )y 1-y
y: 1 ⋅⋅⋅⋅⋅ 0.5 ⋅⋅⋅⋅⋅ 0(1-y) = 0: leucoemeraldine(1-y) = 1: pernigraniline(1-y) = 0.5: emeraldine
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01.02.05 ws 04/05-functional π-systems: part 3 35
Polyaniline – conducting and nonconducting forms
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
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Properties and applications of conducting polymers
pf
Ø nonlinear optical responceØ semiconducting propertiesØ conducting transparent plasticsØ thin-film field-effect transistorsØ light-emitting diodesØ solid-state lasersØ photovoltaic devicesØ chemical sensors
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01.02.05 ws 04/05-functional π-systems: part 3 37
Platonic Symmetry
l / cnf
» Platonische Kohlenwasserstoffe: W. Grahn, Chemie in unserer Zeit1981, 15, 52-61.
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01.02.05 ws 04/05-functional π-systems: part 3 38
Allotropic forms of carbon
diamond graphite Fullerene„truncatedicosahedran“ l / cnf
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01.02.05 ws 04/05-functional π-systems: part 3 39
References on fullerene chemistry
» A. Hirsch, Chemie in unserer Zeit 1994, 28, 79-87.
» A. Hirsch, The Chemistry of the Fullerenes, GeorgThieme Verlag, Stuttgart, 1994.
» M. S. Dresselhaus, G. Dresselhaus, P. C. Eklund,Science of Fullerenes and Carbon Nanotubes, AcademicPress, San Diego, 1996.
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01.02.05 ws 04/05-functional π-systems: part 3 40
Icosahedral symmetry (Ih)
C60 fullerene:A truncated icosaeder
l / cnfØ The Beauty of Symmetry: A. Müller, Science 2003, 300, 749-750.
icosaeder
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01.02.05 ws 04/05-functional π-systems: part 3 41
Some properties of C60
Ø discovered 1985 (Nature 1985, 318, 162)Ø truncated icosahedral structure, Ih symmetryØ 12 pentagonale rings (Euler‘s rule), 20 hexagonale ringsØ substructures: radialene, benzene, corannulene,
pyracyclene; „isolated pentagon rule“Ø strained hydrocarbon, diameter around 7.1 DØ 13C-NMR: one signal, δ = 143 ppm (benzene, 128 ppm)Ø ionization energy around 7.6 eV, electron affinity around
2,7 eV
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01.02.05 ws 04/05-functional π-systems: part 3 42
Electronic structure of C60 fullerene
C60 fullerene:A truncated icosaeder
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01.02.05 ws 04/05-functional π-systems: part 3 43
1,3-Dipoles
C NR
CH2 CN
C
R
H
H+ azomethine ylide
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01.02.05 ws 04/05-functional π-systems: part 3 44
1,3-Dipolar cycloaddition: HOMO-LUMO interaction
» R. Sustmann, Pure and Applied Chemistry 1974, 40, 569-593.
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01.02.05 ws 04/05-functional π-systems: part 3 45
1,3-Dipolar cycloaddition of fullerenes
» D. M. Guldi, et. al,, J. Phys. Chem.B 2003, 107, 7293.
CN
C
R
H
HC
NOH
HC
R
HHH
CO2H+
» M. Prato, M. Maggini, Acc. Chem.Res. 1998, 31, 519.
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01.02.05 ws 04/05-functional π-systems: part 3 46
Functionalized fullerenes
» Die Chemie der Fullerene, A. Hirsch, Chemie in unserer Zeit 1994, 28, 79-87.
N
C5H11
NO2
EtOOC COOEt
1 32
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01.02.05 ws 04/05-functional π-systems: part 3 47
Endohedral fullerenes
Ø encapsulation of molecular hydrogen
» Synthesis of H2@1 : M. Murata, J. Am. Chem. Soc. 2003, 125, 7152.
» Synthesis of H2@2 : K. Komatsu, Science 2005, 307, 238.
H2@2H2@1
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01.02.05 ws 04/05-functional π-systems: part 3 48
Encapsulation of molecular hydrogen in fullerene C60
» K. Komatsu, M. Murata, Y. Murata, Science (Washington,DC, United States) 2005, 307, 238-240.
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01.02.05 ws 04/05-functional π-systems: part 3 49
Nanotubes
» ChemPhysChem 2001, 2, 78-105; Chem. Rev. 1999, 99, 1787-1799. lcnf/sfg
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01.02.05 ws 04/05-functional π-systems: part 3 50
gff_lcnf
Isoalloxazine an important heterocycle in Nature
∗ 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 to the right sideformula)
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01.02.05 ws 04/05-functional π-systems: part 3 51
Flavins: absorption and emission
∗ color of flavin: yellow; color of fluorescence: bright yellow, inaqueous solution, Φf 0.26, pH 7; phosphorescence ( λ ~ 610nm, < 150K, orange-red, ΦP 0.0012)
» P. F. Heelis, Chem. Soc. Rev. 1982, 11, 15-39
fluorescence
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01.02.05 ws 04/05-functional π-systems: part 3 52
Isoalloxazines: Synthetic route
F
NO2
NH2
Br
N
Br
H
NO2
N
NH2
H
Br
N
NO
OO
O
H
H
N
N
N
N O
OH
Br
N
N
N
N O
OCH3
Br
N
N N
N
O
O
OH
H H
H
+KOH/DMSO Zn/AcOH AcOH/H3BO3
H2OK2CO3, CH3I
DMF
HNO3
(Alloxane/Hydrate)
3-Methyl-10-(4-Bromphenyl)-isoalloxazine
» P. Kirsch, et.al., Liebigs Ann. 1995, 1275.
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01.02.05 ws 04/05-functional π-systems: part 3 53
Reduction of the isoalloxazine unit in FAD
N
N
N
N O
OH
R
N
N
N
N O
OH
R H
H
N
N
N
N O
OH
R
H
FADH-FAD
two electronstwo protons
FADH2
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01.02.05 ws 04/05-functional π-systems: part 3 54
Repair of light damaged DNA
» T. Carell, R. Epple, Eur. J. Org. Chem. 1998, 1245-1258.
N
N
N
N O
OH
R
CH3
CH3
H
N
N
N
N O
OH
R
CH3
CH3
H
antenna
excited energy transfer
N
N
O
O
CH3H
P
N
N
O
O
HCH3
N
N
O
O
CH3H
P
N
N
O
O
HCH3 N
N
O
O
CH3H
N
N
O
O
HCH3
P
FADH- FADH-*
*
electron transferelectrontransfer
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01.02.05 ws 04/05-functional π-systems: part 3 55
Ribbon diagram of a DNA photolyase (Eschericia coli)
Science 1995, 268,1866-1872.
αα/ββ domain: whiteMTHF: light grayhelical domain: goldFAD: greenAMP: red
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01.02.05 ws 04/05-functional π-systems: part 3 56
gnl_lcnf
Photolyase dependentrepair of DNA lesion
» Science 1999, 284, 760-765.» Eur. J. Org. Chem. 1998,
1245-1258.
antenna
excitation energy transfer
electron transfer:bond breaking upon reduction
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01.02.05 ws 04/05-functional π-systems: part 3 57
fds_lcnf
Organic light emitting diodes: references
» 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.
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01.02.05 ws 04/05-functional π-systems: part 3 58
fl_lcnf
Organic light emitting diodes (LED): basicprocesses
» Angew. Chem. 1998, 110,416-443.
a: photoluminescence
b: electroluminescence
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01.02.05 ws 04/05-functional π-systems: part 3 59
fds_lcnf
Organic light emitting diodes (LED): polymerblend technology
» Appl. Phys. Lett. 1987,51, 913
» Adv. Mater. 1995, 7,551-554.
» Bunsenges. Phys. Chem.1996, 100, 1667-1677.
Polymer- LED‘s use polymers suchas PPV as electroluminescentmaterials: Nature 1990, 347, 539-541.
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01.02.05 ws 04/05-functional π-systems: part 3 60
fds_lcnf
Organic light emitting diodes (LED): polymer-LED
» Nature 1990, 347, 539-541; Angew. Chem. 1998, 110, 416-443.