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Lecture 2A
2A. Introduction and Synthesis of Important
Conjugated Polymers
Lecture 3
3. Fullerene Chemistry
General Introduction
Solution Polymerization
Oligolyacenes
Types of Polymers
-A-A.A-A.A-A-A-A-
AAAAAAAA H
Homopolymer
l
-A-B-B-A-B-A-A-B-
ABBABAAB Random copolymer
(h)
(a) Star
Star, (b) comb
comb, (c) ladder
ladder, (d) pseudo ladder
ladder, (e) rotaxane
rotaxane, (f) catenane
catenane, (g) dendrimer (h)
rigid rod
Machado J.M.;
Machado, J M ; Masse,
Masse M.A.;
M A ; Karasz,
Karasz F.E.
F E Polymer,
Polymer 1989,
1989 30,
30 1992
Step Growth or Condensation Polymerization
O O O O
H2N(CH2)6NH2 +
Cl (CH2)4 Cl HN(H2C)6-HN (CH2)4
n
A B -(A-B)-n
Nylon 66
Nylon 6
M l K
Mylar, Kevlar,
l K Kapton,
t PPT
PPT, PT
PT, PPy
PP
Carothers Equation
Free Radical
Initiator Δ R O CN
or hν CN
G G O Ph N
Ph O N
R + H2C CH R CH2CH O
G
Initiators:
G G G Thermal
R CH2CH + H2C CH R CH2CH CH2CH
O O
G Ph
G G Ph
Ph
RS-SR
H2C CH Ph
R CH2CH CH2CH [CH2CH(G)]n O
OH
Photochemical
R + HC CH Intractable products
Chain-Growth Polymerization
G
Z-N
H2C CH [[CH2CH(G)]
( )]n
Z-N
Z N
HC CH [CH=CH]n
LnRu=CHPh
-(CH=CH)n
LnRu=CHPh
-(CH=CH-CH=CH-CH=CH-CH=CR)n
QuickTime™ and a
TIFF (Uncompressed) decompressor
LnRu=CHPh = are needed to see this picture.
Suzuki
Cat
Br-Ar-Br + (RO)2BAr'-B(OR)2 (Ar-Ar')n
Heck
Cat
Br-Ar-Br Ar
Ar' Ar'
n
GRIM/Kumada
R R
GRIM
Br Br Cat
X X n
X=S
Sheina, E.E.; Iovu, M.C.; McCullough, R.D. Polym. Prepr. 2005, 46(1), 682
Oxidative (Cationic) Polymerization
R R R R
H
FeIII X -2H
2H X
2 2
-e(-)
X X X X
H
R R
R R R R
X FeIII X X X
X -e(-)
X X X
R R R R
R R R R
X X X
-2H X FeIII
X X X X
R R R
R
X = S, N
Oxidative Polymerization
Thiophene as a “handle”
R R R R
FeIII
X Ar X X Ar X n
Polyaniline
NH2 NH N
(NH4)2S2O8 y
-ee(-) x N
Reductive (Anionic) Polymerization
Br Br O
O
Hg O
O +e(-)
()
n
Br Br
Utley, J.H.; Gao, Y.; Gruber, J.; Zhang, Y.; Munoz-Escalona, A. Chem Mater. 1995, 5, 1837
Reductive Polymerization
Br Br O
O
Hg O
O +e(-)
n
Br Br
B
Br B
Br B
Br O O
O
O O
O Hg Br Hg
+e(-) O +e(-)
()
O
n n
Br Br Br Br
Utley, J.H.; Gao, Y.; Gruber, J.; Zhang, Y.; Munoz-Escalona, A. Chem Mater. 1995, 5, 1837
PPV Synthesis
*
*
Me2S
* = ((-)) or (•)
()
SMe2
+ (CH3)2S
Δ n
n
Processable Polyelectrolyte
Polyacenes??
o yace es??
Acenes
8.0
eV)
MO gap (e
Cl
Closed
d shell
h ll
6.0
Biradical
4.0
HOMO-LUM
2.0
00
0.0
0 2 4 6 8 10
Acene
1.440
1.435
1.430
1.425
1.420 Close shell
1.415 Biradical
1 410
1.410 Ti l t
Triplet
1.405
1.400
1.395
1.390
0 2 4 6 8 10
Acene
Connection Between Band Theory and
Molecular Orbital Theory
According
cco d g to o thee Su
Su-Schrieffer-Heeger
Sc e e eege (SS
(SSH)) model,
ode , thee
effective length of a soliton in a σ-system is about 14 carbon
atoms.
This is in agreement with our calculations, predicting
diradical character in oligoacenes,
g and thus, hexacene-
heptacene have already enough σ -length (two 13-15 carbon
atom chains, respectively) to produce two oligoacetylene
solitons.
lit
Bendikov, M.; Duong, H.M.; Starkey, K.; Houk, K.N.; Carter, E.A.; Wudl, F.; J. Am. Chem. Soc.,
2004, 126(24) 7416
Summary
Marcia M. Payne, Sean R. Parkin, and John E. Anthony 2005, 127, 8028
Marcia M. Payne, Sean R. Parkin, and John E. Anthony 2005, 127, 8028
Marcia M. Payne, Sean R. Parkin, and John E. Anthony 2005, 127, 8028
TIPS ACETYLENE TETRAARYLHEPTACENE ISOLABLE
AND RELATIVELY STABLE
Si(iPr)3 Si(iP )3
Si(iPr) Si
Ph Ph
O Ph Ph
Br a Br c
b
O O
B
Br Br
O Ph Ph
Ph Ph
Si(iPr)3 Si(iPr)3 Si
QuickTime™ and a
TIFF (LZW) decompressor
are needed to see this picture.
Si Si
Ph Ph Ph O Ph
O2
O
hν
Ph Ph Ph Ph
Si Si
LIMITED CYCLIC VOLTAMMETRY
Photoinduced Charge Generation