Novel surfactants for the production of functional nanostructured materials via the ionic self-assembly (ISA) route [Elektronische Ressource] = Neuartige Tenside für die Synthese funktioneller nanostrukturierter Materialien durch ionische Selbsorganisation / von Danielle Franke

Cfranke

Informations

• Publié par: universitat_potsdam
• Publié le: 01 janvier 2006
• Nombre de lectures: 9
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

Max-Planck-Institut für Kolloid- und Grenzflächenforschung
Abteilung Kolloidchemie





Novel Surfactants for the Production of Functional
Nanostructured Materials
via the Ionic Self-Assembly (ISA) Route


Neuartige Tenside für die Synthese Funktioneller
Nanostrukturierter Materialien durch
Ionische Selbsorganisation










Dissertation
zur Erlangung des akademischen Grades
"doctor rerum naturalium"
(Dr. rer. nat.)
in der Wissenschaftsdisziplin Physikalische Chemie






eingereicht an der
Mathematisch-Naturwissenschaftlichen Fakultät
der Universität Potsdam



von
Danielle Franke
Geboren in Leeds, England, am 15. April, 1979



Potsdam, den 7. November 2005




A goal properly set is halfway reached

Abraham Lincoln (1809 - 1865)




TO MY PARENTS

ABSTRACT
In recent years, the aim of supramolecular syntheses is not only the creation of
particular structures but also the introduction of specific functions in these supramolecules.
The present work describes the use of the ionic self-assembly (ISA) route to generate
nanostructured materials with integrated functionality. Since the ISA strategy has proved to
be a facile method for the production of liquid-crystalline materials, we investigated the phase
behaviour, physical properties and function of a variety of ISA materials comprising a
perylene derivative as the employed oligoelectrolyte. Functionality was introduced into the
materials through the use of functional surfactants.

In order to meet the requirements to produce functional ISA materials through the use
of functional surfactants, we designed and synthesized pyrrole-derived monomers as
surfactant building blocks. Owing to the presence of the pyrrole moiety, these surfactants are
not only polymerizable but are also potentially conductive when polymerized. We adopted
single-tailed and double-tailed N-substituted pyrrole monomers as target molecules. Since
routine characterization analysis of the double-tailed pyrrole-containing surfactant indicated
very interesting, complex phase behaviour, a comprehensive investigation of its interfacial
properties and mesophase behavior was conducted. The synthesized pyrrole-derived
surfactants were then employed in the synthesis of ISA complexes. The self-assembled
materials were characterized and subsequently polymerized by both chemical and
electrochemical methods. The changes in the structure and properties of the materials caused
by the in-situ polymerization were addressed.

In the second part of this work, the motif investigated was a property rather than a
function. Since chiral superstructures have obtained much attention during the last few years,
we investigated the possibility of chiral ISA materials through the use of chiral surfactants.
Thus, the work involved synthesis of novel chiral surfactants and their incorporation in ISA
materials with the aim of obtaining ionically self-assembled chiral superstructures.

The results and insights presented here suggest that the presented synthesis strategy can
be easily extended to incorporate any kind of charged tectonic unit with desired optical,
electrical, or magnetic properties into supramolecular assemblies for practical applications.
Contents


1 Introduction..................................................................................................................1
1.1 Supramolecular Chemistry: From Molecule to Material...............................................1
1.1.1 Noncovalent Bonding Strategies.................................................................................................1
1.1.2 Towards Functional Materials.....................................................................................................3
1.2 Conducting polymers.......................................................................................................4
1.2.1 Polypyrrole.................................................................................................................................5
1.2.2 Mechanisms of Conduction.........................................................................................................6
1.2.3 Synthesis of Conducting Polymers............................................................................................11
1.2.3.1 Chemical Synthesis.........................................................................................................11
1.2.3.2 Electrochemical Synthesis...............................................................................................12
1.2.4 Substituted Heterocycles...........................................................................................................14
1.2.5 Soluble conducting pyrrole-based polymers..............................................................................14
1.2.6 Polymerization in Organized Media..........................................................................................15
1.3 Objectives......................................................................................................................17
2 Characterization Methods...........................................................................................19
2.1 X-ray Diffraction...........................................................................................................19
2.2 Circular Dichroism........................................................................................................22
2.3 Polarized Light Microscopy..........................................................................................26
3 Results and Discussion................................................................................................29
3.1 Pyrrole-based surfactants..............................................................................................29
3.1.1 Synthesis..................................................................................................................................29
3.1.1.1 Phase Characterization of Double-tailed surfactant...........................................................30
3.1.2 Complexation with perylene oligoelectrolyte.............................................................................44
3.1.3 Material Characterization..........................................................................................................45
3.1.4 Polymerization.........................................................................................................................52
3.1.4.1 Chemical polymerization.................................................................................................52
3.1.4.2 Electrochemical polymerization.......................................................................................60
3.1.5 Conductive Properties...............................................................................................................62
3.1.6 Conclusion...............................................................................................................................64


3.2 Lysine-based surfactants...............................................................................................65
3.2.1 Synthesis..................................................................................................................................65
3.2.2 Complexation with perylene oligoelectrolyte............................................................................66
3.2.3 Film Characterization...............................................................................................................67
3.2.3.1 UV characterization........................................................................................................67
3.2.3.2 The induction of chirality................................................................................................68
3.2.3.3 Structural analysis...........................................................................................................72
3.2.4 Molecular Modeling Studies.....................................................................................................75
3.2.5 Conclusion...............................................................................................................................76
4 Summary and Outlook................................................................................................78
5 Experimental...............................................................................................................81
5.1 Materials........................................................................................................................81
5.2 Synthetic Procedures.....................................................................................................82
5.2.1 Synthesis of perylene dye derivative.........................................................................................82
5.2.2 Synthesis of surfactants............................................................................................................82
5.2.2.1 Pyrr