cole Polytechnique Fdrale de Lausanne (EPFL)

Institute of Materials (IMX)

Laboratory of Macromolecular and Organic Materials (LMOM)
EPFL - STI - IMX - LMOM
Building MXG, Station 12
1015 Lausanne, Switzerland
holger.frauenrath@ep.ch
Holger Frauenrath
Organic & Macromolecular Chemistry
for Materials Scientists
Introduction
Table of Contents
2
Introduction & Motivation
Part I: Organic Chemistry
1. The Nature of the Covalent Bond
2. Basics of Organic Chemistry
3. Mechanisms of Organic Reactions
4. Selected Classes of Organic Compounds
Part II: Macromolecular Chemistry
5. Basics of Macromolecular Chemistry and Polymer Science
6. Step-Growth Polymerizations
7. Chain-Growth Polymerizations
8. Living and Controlled Polymerizations
9. Selected Classes of Polymers
2 h

2 h
4 h
6 h
2 h

4 h
2 h
2 h
2 h
2 h
Introduction & Motivation
Introduction
Structure Formation on Dierent Length Scales
4
10
10
10
9
10
8
10
7
10
6
10
5
10
4
10
2
10
0
10
3
10
1
size in m
Electron Beam Lithography
Photolithography
Organic Synthesis
Polymer Synthesis
I
n
s
u
l
i
n
H
g
b
R
i
b
o
s
o
m
e
T
M
V
N
u
c
l
e
i
B
a
c
t
e
r
i
a
Photography
E
r
y
t
h
r
o
c
y
t
e
Soft Lithography
Dip-Pen Nanolithography
T
r
y
p
s
i
n
C
o
l
l
a
g
e
n
X-ray UV VIS IR Micro Radio
Micromechanical Engineering
top down
bottom up
Introduction
Research at the Interface of Chemistry and Materials Science
Synthetic
Organic Chemistry
Preparative
Polymer Chemistry
Supramolecular
Chemistry
Sophisticated Molecular Precursors
for Functional Organic Materials
Nanostructured
Carbonaceous Materials
Organic Materials for
Optoelectronics
Hierarchical Structures
from Polymers
Supramolecular
Synthesis Method
Development
Feedback from
Materials Science
and Processing
Molecular Chemistry
Materials Science
5
Introduction
Nanowires from Hydrogen-Bonded p- and n-Type Semiconductors
6

helicity and terminal polymer attachment guide towards dened one-dimensional aggregates
S
4
N
H
O
H
N
O
n
x
N
H
O
H
N
O
n
x
Introduction
Synthesis of the Oligothiophene-Oligopeptide-Polymer (OTOP) Conjugates
7
n = 0, 1, 2, 3
S
4
N
H
O
H
N
O
n
15
N
H
O
H
N
O
n
15
5
BuLi, THF
Br N
Si
Si
HO-Ala
m
-Fmoc
EDCI/HOBt
DIEA, DCM
90100%
NH
2
15
1
toluene
90C, 7 d
100%
NH
2
15
2
PyBOP
DIEA, DCM
80100%
N
H
H
N
O
m
15
Fmoc
3
N
H
H
N
O
m
15
H
4
piperidine
75100%
H
2
, 100 bar
S
4
HO
O
OH
O
Oligothiophene Nanowires
AFM Images
8
!""#$%
n = 0
S
4
N
H
O
H
N
O
n
15
N
H
O
H
N
O
n
15
!"#$
!"#$
n = 3
Oligothiophene Nanowires
ESR Measurements of Degassed Samples
9
S
4
N
H
O
H
N
O
n
15
N
H
O
H
N
O
n
15
3460 3480 3500 3520
magnetic eld / G
E
S
R

s
i
g
n
a
l

(
a
.
u
.
)
n = 0 (100)
n = 1 (100)
n = 2 (100)
n = 3
g = 2.0023
0 50 100 150 200 250 300
T / K
25
0
m
a
g
n
e
t
i
c

s
u
s
c
e
p
t
i
b
i
t
l
i
t
y

(
E
S
R
)

/

a
.
u
.
Pauli behavior
Curie behavior
n = 3
3460 3480 3500 3520
magnetic eld / G
E
S
R

s
i
g
n
a
l

(
a
.
u
.
)
before hydrazine
after hydrazine
after iodine
Stupp S.I. et al. Nature Materials 2010, 9, 594. Perylene Bisimide Nanowires
Microbers Obtained by Solution Spinning
10
N
O
O
N
O
O
N
H
H
N
O
O
N
H
H
N
O
O
19
19
3 3
Microbers Obtained by Solution Spinning
11 Perylene Bisimide Nanowires

many centimeters long uniform microbers obtained by solution spinning

N
O
O
N
O
O
N
H
H
N
O
O
N
H
H
N
O
O
19
19
3 3
Perylene Bisimide Nanowires
SEM of Samples Spun from TCE-Solution into MeOH
12
100 m 20 m 2 m

needle diameter 0.5 mm

uniform microbers (20 m) composed of microbrils (500 nm) and protobrils (70 nm)
N
O
O
N
O
O
N
H
H
N
O
O
N
H
H
N
O
O
19
19
3 3
Laboratory of Polymer and Composite Technology (LTC) Introduction
Novel Materials from Biodegradable Composites
13
1 Proprietary and confidential information
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Supramolecular Nanomaterials and Interfaces Laboratory (SUNMIL) Introduction
Cellular Tracking of Carriers
14

Challenge and fundamental problem for synthetic materials is cell membrane penetration
Verma, Uzun, Irvine, Stellacci, Nature Mat. 2008 Introduction
Cellular Uptake of Nanoparticles
15
All MUS
MUS brOT 2:1 MUS OT 2:1

distribution and structure of amphiphiles on nanoprticles inuences their cellular uptake

CONFIDENTIAL Organic Electronic Materials
Synthesis of a Soluble Quaterthiophene
16
Cl
Cl Cl
Cl
Cl
Cl
O
O
O
S H
2
N S
NBS, DMF
Cl
Cl Cl
Cl
Cl
Cl
N
O
O
toluene
reux
91% (155 g)
+
S
Br
S
SnBu
3
Pd(PPh
3
)
2
Cl
2
DMF
75% (73 g)
Cl
Cl Cl
Cl
Cl
Cl
N
O
O
S
Cl
Cl Cl
Cl
Cl
Cl
N
O
O
S
AgNO
3
, KF
Pd(PhCN)
2
Cl
2
DMSO
60 % (42 g)
S
Cl
Cl Cl
Cl
Cl
Cl
N
O
O
S S
S
Cl
Cl Cl
Cl
Cl
Cl
N
O
O

novel protecting groups for large-scale synthesis, high solubility, good crystallinity

no column chromatography, all intermediates and products puried by recrystallization

Organic Electronic Materials
Evaporation at Low Rates, High Temperatures and with a High Coverage
17
S
S
S
S
H
N
N
H
O
O

slow evaporation at 140C yields continuous layers of epitaxially, layer-by-layer grown lms
1 m
140C 1 /min 1200
A
B
20
0
0 0.2 0.4 0.6 0.8 1
length / m
h
e
i
g
h
t

/

n
m
A
B
~ 3 nm
in collaboration with Stphane Surez, Michel Schaer and Libero Zuppiroli Organic Electronic Materials
Transistor Characteristics
18
120C
60C
20C
I
D
S

/

1
0

3

A

(
V
D

=

6
0

V
)
-60 -50 -40 -30 -20 -10 0
0
5
25
V
Gate
/ V
120C
60C
20C
-60 -40 -20 0 20
V
Gate
/ V
I
D
S

/

A



(
V
D

=

6
0

V
)
6
0
I
D
S

/


A



(
V
D

=

6
0

V
)
-60 -40 -20 0 20
V
Gate
/ V
10
4
10
5
10
9
10
10
120C
60C
20C
T
sub
grain size / nm V
T
/ V I
DS, max
/ A
app
/ cm
2
V
1
s
1
I
on
/I
o
20C <100 4 5.04 10
8
3.47 10
5
130
60C 250 25 7.52 10
7
6.11 10
3
4,200
120C 3,500 9 2.30 10
5
1.84 10
2
45,600