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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

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Introduction & Motivation

Introduction

Structure Formation on Different Length Scales

4

1010 109 108 107 106 105 104 102 100103 101

size in m

Electron Beam Lithography

Photolithography

Organic Synthesis

Polymer Synthesis

Insuli

nHg

b

Ribosome TM

VNu

clei

Bacteria

Photography

Erythr

ocyte

Soft Lithography

Dip-Pen Nanolithography

Trypsin

Colla

gen

X-ray UV VIS IR Micro Radio

Micromechanical Engineering

top down

bottom up

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Introduction

Research at the Interface of Chemistry and Materials Science

SyntheticOrganic Chemistry

PreparativePolymer Chemistry

SupramolecularChemistry

Sophisticated Molecular Precursorsfor Functional Organic Materials

NanostructuredCarbonaceous Materials

Organic Materials forOptoelectronics

Hierarchical Structuresfrom Polymers

SupramolecularSynthesis MethodDevelopment

Feedback fromMaterials Science

and Processing

Molecular Chemistry

Materials Science

5

Introduction

Nanowires from Hydrogen-Bondedp- and n-Type Semiconductors

6

helicity and terminal polymer attachment guide towards defined one-dimensional aggregates

S4

NH

OHN

On

x

NH

OHN

On

x

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Oligothiophene Nanowires

ESR Measurements of Degassed Samples

9

S4

NH

OHN

On

15

NH

O HN

On

15

3460 3480 3500 3520magnetic field / G

ESR

signal(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

magneticsusceptibitlity(ESR)/a.u.

Pauli behavior

Curie behavior

n = 3

3460 3480 3500 3520magnetic field / G

ESR

signal(a.u.

)

before hydrazine

after hydrazineafter iodine

Stupp S.I. et al. Nature Materials 2010, 9, 594.Perylene Bisimide Nanowires

Microfibers Obtained by Solution Spinning

10

N

O

O

N

O

O

NH

HN

O

O

NH

HN

O

O

19 1933

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Microfibers Obtained by Solution Spinning

11Perylene Bisimide Nanowires

many centimeters long uniform microfibers obtained by solution spinning

N

O

O

N

O

O

NH

HN

O

O

NH

HN

O

O

19 1933

Perylene Bisimide Nanowires

SEM of Samples Spun from TCE-Solution into MeOH

12

100m 20 m 2 m

needle diameter 0.5 mm uniform microfibers (20 m) composed of microfibrils (500 nm) and protofibrils (70 nm)

N

O

O

N

O

O

NH

HN

O

O

NH

HN

O

O

19 1933

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Laboratory of Polymer and Composite Technology (LTC)Introduction

Novel Materials from Biodegradable Composites

13

!"#$%#&'()#*+),-+.$,/&-',(&)0+&,/$#1)(&$,

!"#$%&'"(()$*)+

!"#$%&'(

2','3)40'+1)('#&)05 6#'',+%#$.'55&,7+ 8(#9.(9#)0+.$,(#$0+ 8(#9.(9#'+: %#$%'#(*+0&,;

!"#$"%&'(&)*

,#+-).+#/$%"$,%

&/0-"1#2#(#13%

4./&)++#$*5%%

&/$1./(%/6%

$7&()"1#/$%"$,%

*./81'%%/6%

2722()+

4./-).1#)+5%",)97"1)%

&/0-./0#+)%2)18))$%

2#/,)*.","2#(#13%"$,%+1"2#(#13

:#/-/(30).%;4

?//,%6#2.)+

@"$/&)((7(/+)

A/00#$*(#$* B7-).&.#1#&"(%ACDB1#66$)++ #$&.)"+)

@)8%6/"0+

A/$E)$1#/$"(%

6/"0+

($from

Supramolecular Nanomaterials and Interfaces Laboratory (SUNMIL)Introduction

Cellular Trafficking of Carriers

14

Challenge and fundamental problem for synthetic materials is cell membrane penetration

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Organic Electronic Materials

Evaporation at Low Rates, High Temperatures and with a High Coverage

17

S

S

S

S

HN

NH

O

O

slow evaporation at 140C yields continuous layers of epitaxially, layer-by-layer grown films

1 m

140C 1 /min 1200

A

B

20

00 0.2 0.4 0.6 0.8 1

length / m

height/nm

A

B

~ 3 nm

in collaboration with Stphane Surez, Michel Schaer and L ibero ZuppiroliOrganic Electronic Materials

Transistor Characteristics

18

120C

60C

20C

IDS

/

10

3A

(VD=6

0V)

-60 -50 -40 -30 -20 -10 0

0

5

25

VGate

/ V

120C

60C

20C

-60 -40 -20 0 20

VGate

/ V

IDS

/A

(VD

=6

0V)

6

0

IDS/

A

(VD=6

0V)

-60 -40 -20 0 20

VGate

/ V

104

105

109

1010

120C

60C

20C

Tsub grain size / nm VT/ V IDS, max/ A app / cm2V1s1 Ion/Ioff

20C