La lecture à portée de main
218
pages
Deutsch
Documents
2008
Écrit par
Feng
Publié par
johannes_gutenberg-universitat_mainz
Obtenez un accès à la bibliothèque pour le consulter en ligne En savoir plus
Découvre YouScribe en t'inscrivant gratuitement
Découvre YouScribe en t'inscrivant gratuitement
218
pages
Deutsch
Ebook
2008
Obtenez un accès à la bibliothèque pour le consulter en ligne En savoir plus
Publié par
Publié le
01 janvier 2008
Nombre de lectures
23
Langue
Deutsch
Poids de l'ouvrage
16 Mo
Publié par
Publié le
01 janvier 2008
Nombre de lectures
23
Langue
Deutsch
Poids de l'ouvrage
16 Mo
C -symmetric Discotic Liquid Crystalline 3
Materials for Molecular Electronics:
Versatile Synthesis and Self-organization Versatile Synthesis and Self-organization
Dissertation Dissertation
zur Erlangung des Grades
“Doktor der Naturwissenschaften”
dem Fachbereich Chemie und Pharmazie der
Johannes Gutenberg-Universität Mainz
vorgelegt von
Xinliang Feng
geboren in Anhui Province / P. R. China
Mainz, 2008
Decan: Herr Prof. Dr.
1. Berichterstatter: Herr Prof. Dr. 1. Berichterstatter: Herr Prof. Dr.
2. Berichterstatter: Herr Prof. Dr.
Tag der mündlichen Prüfung:
Die vorliegende Arbeit wurde in der Zeit von September
2004 bis Februar 2008 im Max-Planck-Institut für 2004 bis Februar 2008 im Max-Planck-Institut für
Polymerforschung in Mainz unter Anleitung von Herrn Prof.
Dr. Müllen ausgeführt.
Ich danke Herrn Prof. Dr. K. Müllen für seine Ich danke Herrn Prof. Dr. K. Müllen für seine
wissenschaftliche und persönliche Unterstützung sowie für
seine ständige Diskussionsbereitschaft. Table of Contents
Table of Contents
Chapter 1. Introduction......................................................................................1
1.1. Polycyclic Aromtaic Hydrocarbons...……….....................…....…………. ..1
1.1.1. Synthesis………………………..…………………………………………………….3
1.1.1.1. Intra- and intermolecular Diels-Alder reaction………………...…………………...3
1.1.1.2. Ring-closing olefin metathesis (RCM)……………………………………..………5
1.1.1.3. Benzannulation and electrophilic cyclization…………………………….………...6
1.1.1.4. Intramolecular photocyclization of stilbene type compounds….…………………..7
1.1.1.5. Flash vacuum pyrolysis…………………………………………………………….8
1.1.1.6. Oxidative cyclodehydrogenation……………………………………………….…..9
1.2. Self-organization and Discotic Liquid Crystals……...…………...…….....11
1.2.1. Introduction and materials………………………………………………………...…11
1.2.2. Characterization of the self-organization…………..………………………………..15
1.2.3. Self-assembly of discotics on the surface……………………………………………17
1.2.4. DLCs for electronic devices………………………………………………………….19
1.2.4.1. Organic field effect transistors (OFETs)…………………………………………...20
1.2.4.2. Bulk heterojunction photovoltaic cells……………………………………….…….21
1.2.4.3. Organic light emitting diodes (OLEDs)……………………………………………21
1.3. Motivation……………………………………………………………..…..22
1.4. References..………………………………………………………………..27
Chapter 2. The Role of Oligophenylene Precursors for Oxidative
Cyclodehydrogenation and Unusual Symmetry Effect on Thermal Behavior
and Self-assembly of Hexa-peri-hexabenzocoronene.....................................34
2.1. Hexa-peri-hexabenzocoronenes by Efficient Oxidative
Cyclodehydrogenation—the Role of the Oligophenylene Precursors…….…....34
2.1.1. Introduction…………………………….......……………...……………………….34
2.1.2. Synthesis…………..……………………………………………………………….36
2.1.3. Summary……………… ………………………………………………………….41
2.2. Unusual Symmetry Effect on Thermal behavior and Self-assembly of Hexa-
peri-hexabenzocoronene……………………………………..……………..….41
I 2.2.1. Introduction…………..………….......………………….....……………………….41
2.2.2. Synthesis…………………………………………………………………………...43
2.2.3. Thermal behavior and self-assembly at the solid-liquid interface…………………44
2.2.4. Summary…………………………………………………………………………...49
2.2.5. References………………………………………………………………………….50
Chapter 3. C symmetric Hexa-peri-hexabenzocoronenes with Alternating 3
Polar/Apolar Substituents…………………...………………………………..53
3.1. Controlling Columnar Orientation of C –symmetric “Superbenzenes” by 3
Alternating Polar/Apolar Substituents..........………………………………. 53
3.1.1. Introduction…………..………….......………………….....……………………….53
3.1.2. Synthesis, structure characterization and self-aggregation in solution…..………...54
3.1.3. Bulk characterization in the solid state……………………………….……………61
3.1.4. Self-assembly in solution and on the surface……………………………………...64
3.1.5. Conclusion...……………………………………………………………………….68
3.2. Synthesis, Helical Organization, and Long-range Fibrous Assembly of C 3
symmetric Hexa-peri-hexabenzocoronene with Methoxy groups………..…68
3.2.1. Introduction…………..………….......………………….....……………………….68
3.2.2. Synthesis and self-assembly in the solution……………………………...………...70
3.2.3. Bulk characterization and self-assembly on the surface…..………….……………73
3.2.4. Conclusion……………………………………….………………………………...77
3.2.5. References...……………………………………………………………… ……….77
Chapter 4. Triangle-shaped Polycyclic Aromatic Hydrocarbons..............81
4.1. Versatile Synthesis and Self-assembly of Triangle-shaped Polycyclic
Aromatic Hydrocarbons…………………………………………….…………..81
4.1.1. Introduction…………..………….......………………….....……………………….81
4.1.2. Synthesis and structure characterization………………………………….………..84
4.1.3. Bulk characterization and self-assembly at solid-liquid interface…………………94
4.1.4. Conclusion…………………………………….…………………………………...98
II Table of Contents
4.2. Supramolecular Organization and Photovoltaics of Triangle-shaped Discotic
Graphenes with Swallow-tailed Alkyl Substituents……………...……….....…98
4.2.1. Introduction…………..………….......………………….....……………………….99
4.2.2. Synthesis and structure characterization………………...……………….……….101
4.2.3. Bulk characterization ……………………………………………..………...……104
4.2.4. Photovoltaic device characterizations…….……………………………………....107
4.2.5. Conclusion………………………………………………………………………..110
4.2.6. References………………………………………………………………………...111
Chapter 5. Controlling the Helical and Staggered Stacking of
Nanographenes……………………………………………………………....116
5.1. From Helical to Staggered Stacking of Biszigzag Nanographenes………117
5.1.1. Introduction…………..………….......………………….....……………………...117
5.1.2. Synthesis and structure characterizations……………………………….………...117
5.1.3. Self-organization in the bulk………………………………………..………….…121
5.1.4. Conclusion…………………………………….………………………………….125
5.2. Rational Design of the Shape and periphery of Discotic Liquid Crystals: a
synthetic way towards high charge carrier mobilities…………………..…….126
5.2.1. Introduction…………..………….......………………….....……………………...126
5.2.2. Synthesis and structure characterization………………………….…….………...131
5.2.3. Bulk characterizations……………………………………..…………………..…133
5.2.4. Computer simulations...……………………….………………………………….135
5.2.4.1. Molecular model and simulation details………………………………………..135
5.2.4.2. Results and discussion………………………………………………………….136
5.2.5. Charge transport…………………………………………………………………..140
5.2.6. Conclusion………………………………………………………………………..141
5.2.7. References………………………………………………………………………...141
Chapter 6. Summary and Outlook…………………………………….…...145
Chapter 7. Experimental Section...………………………………………....153
IIIPublication List………………………………………………………………211
Curriculum Vitae.............................................................................................212
Acknowledgments............................................................................................213
IV Index of Abbreviations
2D-WAXS two-dimensional wide angle X-ray scattering
AFM atomic force microscopy
DCM dichloromethane
DSC differential scanning calorimetry
EA elemental analysis
FD MS field desorption mass spectroscopy
FET field effect transistor
HBC hexa-peri-hexabenzocoronene
HOMO highest occupied molecular orbital
h hour
LED light emitting diode
LUMO lowest unoccupied molecular orbital
MeOH methanol
MS mass spectroscopy
min minute
m.p. melting point
MALDI-TOF matrix-assisted laser desorption ionization –time of flight
NMR nuclear magnetic resonance
PE petroleum ether
PAH polycyclic aromatic hydrocarbons
POM polarized optical microscopy
RT room temperature
STM scanning tunneling microscopy
TCNQ 7,7,8,8-tetracyanoquinodimethane
THF tetrahydrofuran
TLC thin layer chromatography
TMS trimethylsilyl
Tolane diphenylacetylene
UV-vis ultraviolet/visible Introduction