LINZ LECTURES

Lecture 1. The Development of Organic Conductors:

M t l Superconductors
Metals, S d t and
d Semiconductors
S i d t

Lecture 2A
2A. Introduction and Synthesis of Important
Conjugated Polymers

Lecture 2B. Solid State Polymerization

Lecture 3
3. Fullerene Chemistry

Lecture 3B. Molecular Engineering

g g
 Introduction and Synthesis of
Important Conjugated Polymers
Linz, June 10, 2008

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

-A-B-A-B-A-B-A-B- Alternating copolymer

-A-A-A-A-B-B-B-B- Block copolymer

-A-A-A-A-A-A-A-A Graft copolymer

|
B-B-B-B-B-B

Malcolm P. Stevens “Polymer Chemistry: an Introduction” 3rd Ed. Oxford, 1999

 Types of Chains

(a) Linear chain, (b) branched chain, (c) network

Malcolm P. Stevens “Polymer Chemistry: an Introduction” 3rd Ed. Oxford, 1999

 Types of Architectures

(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

Malcolm P. Stevens “Polymer Chemistry: an Introduction” 3rd Ed. Oxford, 1999

Malcolm P. Stevens “Polymer Chemistry: an Introduction” 3rd Ed. Oxford, 1999
“For drawn samples, values for the Young's modulus as high as 37 GPa and
tensile strength
g upp to 500 MPa have been measured in the machine direction.
These properties approach those of many high performance fibers.”

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

H2N(CH2)5 CO2H HN(H2C)5-

n
A -(A-)n

Nylon 6

M l K
Mylar, Kevlar,
l K Kapton,
t PPT
PPT, PT
PT, PPy
PP
 Carothers Equation

Malcolm P. Stevens “Polymer Chemistry: an Introduction” 3rd Ed. Oxford, 1999

 Chain Growth or Addition Polymerization

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

Malcolm P. Stevens “Polymer Chemistry: an Introduction” 3rd Ed. Oxford, 1999

 Ziegler-Natta Polymerization

G
Z-N
H2C CH [[CH2CH(G)]
( )]n

Z-N: Ti(OR)4 AlR3

Z-N
Z N
HC CH [CH=CH]n

Anionic, Cationic, Living

 Ring Opening Metathesis Polymerization (ROMP)

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.

Scherman O. A; Rutenberg I. M; Grubbs R. H J. Am. Chem. Soc. 2003, 125, 8515

 Organometallic Methods:
Kumada, Yamamoto, Colon
Cat
Br-Ar-Br (Ar)n
Cat: PdL4, NiL2

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

SMe2 SMe2 SMe2

*
*
Me2S

* = ((-)) or (•)
()

SMe2

+ (CH3)2S
Δ n
n

Processable Polyelectrolyte

P. M. Lahti, D. A. Modarelli, F. R. Denton, III, R. W. Lenz, F. E. Karasz J. Am. Chem. Soc.

1988, 110, 7258
L. Hontis, V. Vrindts, D. Vanderzande, L. Lutsen Macromolecules, Vol. 36, No. 9, 2003
Thee Last
ast C
Challenge:
a e ge
Linear Polyacenes
y
The Lower Oligoacenes

Polyacenes??
o yace es??
 Acenes

Surprisingly, we have discovered that at the

RB3LYP/6-31G(d) level of theory, the wave
function for as small an oligoacene as triplet

hexacene (and all longer oligoacenes) becomes

unstable. close shell
Re-optimization
Re-optimization, using the unrestricted
open shell
broken symmetry B3LYP method (UB3LYP),
leads to a singlet
g state with largeg amounts of
diradical character.
 HOMO LUMO G
HOMO-LUMO Gap iin Acenes
A

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

Plateau at ca. 1.8 eV

Bendikov, M.; Duong, H.M.; Starkey, K.; Houk, K.N.; Carter, E.A.; Wudl, F.; J. Am. Chem. Soc.,
2004, 126(24) 7416
 A
Acenes, tterminal
i l bond
b d

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

The instabilities found for heptacene-octacene appear to

indicate that they are the “connector” between band theory
and molecular orbital theory.y
Heeger, A. J.; Kivelson, S.; Schrieffer, J. R.; Su, W.-P. Rev. Mod. Phys. 1988, 60, 781.
 Spin
p Density
y

Bendikov, M.; Duong, H.M.; Starkey, K.; Houk, K.N.; Carter, E.A.; Wudl, F.; J. Am. Chem. Soc.,
2004, 126(24) 7416
 Summary

In contrast to the common view that acenes are closed shell

systems or have triplet ground states, we predict that larger
oligoacenes possess an open-shell singlet ground state,
where the triplet lies above singlet.

We have shown computationally that oligoacenes and

probably
p y a varietyy of p
polyacene
y derivatives and analogues
g
should exhibit a nonzero band gap.

It should be possible to prepare a linear polyacene, provided

it is formed as a solid, with minimum lifetime in solution. In
analogy with oligoenes vs polyacetylene.
polyacetylene
EXPERIMENTAL RESULTS
 Matrix Isolated Heptacene

R. Mondal, B. K. Shah, D. C. Neckers J. Am. Chem. Soc. 2006, 128, 9612

R. Mondal, B. K. Shah, D. C. Neckers J. Am. Chem. Soc. 2006, 128, 9612
 Isolable But Very Short-Lived Substituted Heptacene

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

a, (i) TipsCCLi (ii) SnCl2; b, LTMP/DPIBF; c, Zn/AcOH

D. Chun, F. Wudl, unpublished

 CRYSTAL STRUCTURE OF BIS(TIPSTHYNYL)
TETRAPHENYL HEPTACENE

QuickTime™ and a
TIFF (LZW) decompressor
are needed to see this picture.

D. Chun, F. Wudl, unpublished

Electronic Spectroscopy
PHOTOINDUCED OXYGEN DEGRADATION

Si Si

Ph Ph Ph O Ph
O2
O
hν
Ph Ph Ph Ph

Si Si
LIMITED CYCLIC VOLTAMMETRY
 Photoinduced Charge Generation

H. F. Bettinger, R. Mondalb and D. C. Neckers Chem. Commun., 2007, 5209