Heteroatom containing polycyclic aromatic hydrocarbons with positive charge [Elektronische Ressource] : synthesis and characterization / vorgelegt von Dongqing Wu

Wud

Informations

• Publié par: johannes_gutenberg-universitat_mainz
• Publié le: 01 janvier 2008
• Nombre de lectures: 38
• Langue: Deutsch
• Poids de l'ouvrage: 24 Mo

Extrait

Heteroatom Containing Polycyclic
Aromatic Hydrocarbons with
Positive Charge - Synthesis and
Characterization
Dissertation
zur Erlangung des Grades
“Doktor der Naturwissenschaften”
dem Fachbereich Chemie und Pharmazie der
Johannes Gutenberg-Universität Mainz
vorgelegt von
Dongqing Wu
geboren in Henan Province / P. R. China
Mainz, 2008Decan: 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 August 2004
bis Mai 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
wissenschaftliche und persönliche Unterstützung sowie für
sein ständige Diskussionsbereitschaft.Content
Chapter 1. Introduction......................................................................................... 1-38
1.1 Aromaticty and aromatic compounds .............................................................. 1-3
1.2 Polycyclic aromatic hydrocarbons (PAHs).................................................... 3-19
1.2.1 Synthesis of PAHs................................................................................. 4-12
1.2.1.1 Flash vacuum pyrolysis (Thermolysis)........................................ 5-7
1.2.1.2 Friedel-Crafts condensation......................................................... 7-8
1.2.1.3 Acidic cyclodehydration and dehydrogenation of alkylated
enamines .................................................................................................. 8-9
1.2.1.4 Photocyclization......................................................................... 9-10
1.2.1.5 Inter- and intra-molecular Diels-Alder cycloaddition.............. 10-11
1.2.1.6 Oxidative cyclodehydrogenation ............................................. 11-12
1.2.1.7 Other synthetic methods towards PAHs.........................................12
1.2.2 Supramolecular chemistry of PAHs.................................................... 12-17
1.2.2.1 Discotic liquid crystals from PAHs ......................................... 13-14
1.2.2.2 Self-assembly of PAHs in solution .......................................... 14-16
1.2.2.3 Monolayers of PAHs................................................................ 16-17
1.2.3 Electronic devices from PAHs ............................................................ 17-19
1.3 Heteroatom containing polycyclic aromatic hydrocarbons (HPAHs).......... 19-26
1.3.1 Synthesis of HPAHs............................................................................ 20-25
1.3.1.1 Photocyclization ...................................................................... 20-21
1.3.1.2 Intramolecular quaternization.................................................. 21-22
1.3.1.3 Condensation ........................................................................... 22-23
1.3.1.4 Oxidative cyclodehydrogenation ............................................. 23-24
1.3.2 Properties and application of HPAHs ................................................. 25-26
1.3.2.1 Physical properties and aggregation behavior of HPAHs..............25
1.3.2.2 HPAH based organometallic complexes........................................26
1.3.2.3 FETs from HPAHs .........................................................................26
1.4 Motivation and objective ............................................................................. 26-30
References......................................................................................................... 31-38
Chapter 2. Synthesis and Self-assembly of Centrally Charged Nitrogen
Containing Polycyclic Aromatic Hydrocarbons................................................ 39-79
2.1 Introduction.................................................................................................. 39-41
I2.2 Synthesis and characterization of 2-phenyl-benzo[8,9]quinolizino[4,5,6,7-fed]-
phenanthridinylium (PQP) derivates.................................................................. 41-52
2.2.1 General method to synthesize PQP salts............................................. 41-43
2.2.2 Synthesis of alkylated PQP derivates.................................................. 43-45
2.2.3 Synthesis and characterization of 2-phenyl-naphthacene[1,2]quinolizino-
[3,4,5,6-def]benzo[i]phenanthridinium (DBPQP) derivates........................ 45-51
2.2.4 UV-vis and fluorescence spectra of PQP and DBPQP salts................ 51-52
2.3 Self-assembly behavior of PQP and DBPQP salts....................................... 53-73
2.3.1 The effect of alkyl chains.................................................................... 53-63
2.3.2 The effect of counterions 63-68
2.3.3 The size and shape of aromatic cores.................................................. 68-73
2.4 Conclusions.................................................................................................. 73-74
References......................................................................................................... 75-79
Chapter 3. Oxygen and Sulfur Containing Polycyclic Aromatic Hydrocarbons
with Positive Charge: Synthesis and Characterization .................................. 80-107
3.1 Introduction 80-82
3.2 Synthesis and characterization..................................................................... 82-97
3.2.1 Synthesis of benzo[5,6]naphthaceno[1,12,11,10-jklmna]xanthylium
(BNAX) salts ............................................................................................... 82-92
3.2.1.1 Synthesis of BNAX derivates with bromide as anion ............. 82-86
3.2.1.2 Synthesis of BNAX derivates with other anions ..................... 86-88
3.2.2 Synthesis of dibenzo derivate of BNAX salts..................................... 88-92
3.2.3 1,10-jklmna]thioxanthylium
(BNATX) salts ............................................................................................. 93-95
3.2.4 UV-vis absorption and fluorescence of BNAX and BNATX salts ..... 95-97
3.3 Supramolecular behavior of BNAX salts................................................... 97-105
3.3.1 Discotic liquid crystalline from BNAX salts .................................... 97-102
3.3.2 Self-assembly of BNAX salts in solution ....................................... 102-105
3.4 Conclusions.............................................................................................. 105-106
References..................................................................................................... 107-110
Chapter 4. Versatile Synthesis of Nitrogen Containing PAHs with Positive
Charge via Dibenzo[a,j]xanthenylium Salts .................................................. 111-123
4.1 Introduction...............................................................................................111-112
4.2 Synthesis and characterization................................................................. 112-118
II4.2.1 Literature reported synthetic method toward dibenzo[jk,mn]naphtha-
[2,1,8-fgh]thebenidinium (DBNT) salt .................................................... 112-113
4.2.2 New synthetic strategy for DBNT dreivates ................................... 114-120
4.2.3 UV-vis absorption and fluorescence spectra of DBNT salts........... 120-121
4.3 Self-assembly of DBNT salts................................................................... 121-124
4.4 Conclusions.............................................................................................. 124-125
References..................................................................................................... 126-128
Chapter 5. Ionic Self-assembly of Nitrogen Containing Polycyclic Aromatic
Hydrocarbons with Positive Charge .............................................................. 129-145
5.1 Introduction 129-133
5.1.1 Ionic self-assembly (ISA) ............................................................... 129-131
5.1.2 ISA of nitrogen containing PAHs with positive charge .................. 131-133
5.2 ISA of PQP salts....................................................................................... 133-143
5.2.1 ISA of PQP salts and anionic surfactants........................................
5.3 Conclusions......................................................................................................143
References..................................................................................................... 144-145
Chapter 6. Summary and outlook .................................................................. 146-151
6.1 Summary of results .................................................................................. 146-147
6.2 Outlook toward further work ................................................................... 147-150
References.............................................................................................................151
Chapter 7. Experiment part............................................................................ 152-207
Curriculum Vitae .....................................................................................................208
Acknowledgments ...........................................................................