Das Hauptthema dieser Dissertation ist die Untersuchung der Selbstorganisation organischer Moleküle an der Flüssig-Fest-Grenzfläche (LSI). Besondere Betonung liegt auf der Kontrolle der Selbstassemblierung durch geeignete Parameter: die Substrattemperatur während der Abscheidung, die Konzentration der gelösten Moleküle, und die chemische Natur der gelösten Stoffe und Lösungsmittel. Die Untersuchungen wurden unter Verwendung der Rastertunnelmikroskopie (STM) durchgeführt. Der erste Schwerpunkt dieser Arbeit ist die systematische Untersuchung der Auswirkung erhöhter Substrattemperatur während der Abscheidung aus der Lösung auf die Selbstorganisation komplexer molekularer Architekturen an der LSI. Diese Untersuchungen wurden mit dem planaren Molekül Trimesinsäure (TMA), sowie dem nicht-planaren Molekül Benzen-1,3,5-triphosphonsäure (BTP) durchgeführt. Es wird gezeigt, dass der Polymorphismus der Adsorbatstrukturen von TMA und BTP durch die Substrattemperatur während der Abscheidung der Moleküle aus der Lösung für verschiedene Lösungsmitteln unterschiedlicher Polarität, wie Phenyloctan, Octansäure und Undecanol, kontrolliert werden kann. Durch die Erhöhung der Temperatur des vorgeheiztem Graphitsubstrates kann die spezifische 2D supramolekulare Struktur and die entsprechende Packungsdichte der Moleküle in der Adsorbatschicht für jedes der untersuchten Lösungsmittel präzise eingestellt werden. Weiterhin wird der Einfluss der Konzentration auf die resultierende Anordnung der TMA Moleküle an der LSI durch ein weiteres Experiment abgeschätzt, bei welchem Rühren (von 0 h bis 40 h) der Lösungen mit verschiedenen Lösungsmitteln eingesetzt wurde. Diese Ergebnisse zeigen, dass die verschiedenen Präparationsmethoden (Erhöhung der Abscheidetemperatur oder Rühren) zu derselben Tendenz der Änderung der geordneten Strukturen sowie der Packungsdichte führt, weswegen man schlussfolgern kann, dass die Erhöhung der Konzentration an der LSI bei erhöhter Abscheidetemperatur ebenso der Hauptgrund für die beobachteten Änderungen ist. Der zweite Schwerpunkt dieser Dissertation ist die Untersuchung von chemischen Reaktionen der selbstassemblierenden Moleküle. Eine Veresterungsreaktion von TMA mit Undecanol wurde gefunden. Weiterhin wurde, als ein erster Schritt zur Untersuchung der Zwillingspolymerisation, die Oligomerisation des Zwillingsmonomers 2,2’-spirobi [4H-1,3,2-benzo-dioxasiline] (SBS) mit STM an der Grenzfläche zwischen der SBS-Undecanol-Lösung und einer Graphitoberfläche untersucht. Erstens wurde durch Ultraschallbehandlung der SBS Lösung in Undecanol für verschieden lange Zeiten die Oligomerisation der SBS Monomere ohne einen Katalysator an der LSI beobachtet. Zweitens konnte die Oligomerisation auch durch Erhöhung der Substrattemperatur während der Abscheidung der Moleküle aus der Lösung initiiert werden. Durch die schrittweise Erhöhung der Temperatur des vorgeheizten Substrates konnten mehrere, verschiedene, periodische Anordnungen von Phenol‒Dimeren, ‒Trimeren, und –Pentameren u.s.w. gefunden werden. Weiterhin wird die Auswirkung der Abscheidetemperatur auf die Selbstorganisation an der LSI nur der Lösungsmittelmoleküle aus dem reinen Lösungsmittel beschrieben. Dies ist wichtig, da die Undecanol‒Moleküle stets mit den gelösten, in dieser Arbeit verwendeten Stoffen (TMA, BTP, SBS) koadsorbieren und lineare Muster bilden.:Chapter 1: Introduction
Chapter 2: Basic principle
2.1 Principles of scanning tunneling microscopy (STM)
2.1.1 General working principle
2.1.2 Tunneling effect
2.1.3 Theory of STM
2.1.4 Contrast mechanism of molecular adsorbates
2.1.5 Modes of STM operation
2.2 STM at the liquid-solid interface (LSI)
2.3 Thermodynamics and kinetics
2.3.1 Equilibrium of the adsorption/desorption and initial agglomeration at the LSI
2.3.2 Kinetic and thermodynamic control over 2D molecular self-assembly
2.4 Experimental condition
2.4.1 Role of solvent
2.4.2 Role of concentration
2.4.3 Role of temperature
References
Chapter 3: Experimental section
3.1 Solutes
3.1.1 Trimesic acid (TMA) (1,3,5?C6H3(COOH)3)
3.1.2 Benzene 1.3.5-Triphosphonic acid (BTP) (1,3,5?C6H3(PO3H2)3)
3.1.3 Twin monomer 2,2’-spirobi[4H-1,3,2-benzo-dioxasiline] (SBS)
3.2 Solvents
3.3 Substrate: Highly oriented pyrolytic graphite (HOPG (0001))
3.4 Preparation of the STM tips
3.5 Experimental methods for sample preparation
3.5.1 Preparation of the solution
3.5.2 Heating of the substrate
3.5.3 Ultrasonication
3.5.4 Stirring
3.6 Computational details
References
Chapter 4: Deposition temperature? and solvent-dependent 2D supramolecular assemblies of trimesic acid at the liquid-graphite interface revealed by STM
Results and discussion
4.1 Hydrogen bonding motifs of trimesic acid molecules
4.2 TMA deposited from solution in octanoic acid
4.3 TMA deposited from solution in phenyloctane
4.4 TMA deposited from solution in undecanol
4.6 Discussion of the solute–solvent interactions
4.5 Effect of the deposition substrate temperature on the formation of ester at the LSI of TMA in undecanol
Conclusion
References
Chapter 5: Role of concentration on the self-assembly of TMA at the LSI influenced by stirring time
Results and discussion
5.1 TMA in octanoic acid
5.2 TMA in phenyloctane
5.3 TMA in undecanol
Conclusion
References
Chapter 6: Role of deposition temperature on the self-assembly of the non-planar molecule benzene- 1,3,5- triphosphonic acid (BTP) at the LSI
Results and discussion
6.1 BTP in undecanol at room temperature
6.2 BTP in undecanol at high substrate temperature during deposition
Conclusion
References
Chapter 7: Role of deposition temperature on the self-assembly of pure undecanol solvent at the LSI
Results and discussion
7.1 Adsorption geometry of undecanol on HOPG
7.2 Herringbone structures of undecanol
7.3 Parallel structure of undecanol at high substrate temperature during deposition
Conclusion
References
Chapter 8: A first step to microscopically study twinpolymerization: self-assembly of twin monomer 2,2’-Spirobi[4H-1,3,2-benzo-dioxasiline] (SBS) at the LSI influenced by ultrasonication and deposition substrate temperature
8.1 Coadsorption of SBS and undecanol without ultrasonication and at room temperature
8.2 SBS deposited from solution in undecanol in dependence on the duration of ultrasonication
8.3 SBS deposited from solution in undecanol
at varied deposition temperature of the substrate
8.4 Discussion and open questions
Appendix
References
CHAPTER 9: SUMMARY AND OUTLOOK
ERKLÄRUNG
CURRICULUM VITAE
ACKNOWLEDGEMENT / The main aim of this thesis is to study the self-assembly of organic molecules at the liquid-solid interface (LSI). Special emphasis is given to controlling the process of self-assembly via suitable parameters such as: the substrate temperature during the initial deposition, the concentration of dissolved molecules, or the chemical nature of solutes and solvents. The investigations are performed using scanning tunneling microscopy (STM). The first focus of this work is the systematic investigation of the effect of the substrate temperature during the deposition out of the solution on the self-assembly of complex molecular architectures at the LSI. These investigations have been done with the planar molecule trimesic acid (TMA), and the non-planar molecule benzene 1,3,5-triphosphonic acid (BTP). We show that the polymorphism of the adsorbate structures of TMA (also with BTP) can be controlled by the substrate temperature during the deposition of the molecules out of the solution for various solvents of different polarity such as phenyloctane, octanoic acid, and undecanol. By increasing the temperature of the pre-heated graphite substrate, the specific 2D supramolecular structure and the corresponding packing density in the adsorbate layer can be precisely tuned for each kind of the solvents studied. Furthermore, the influence of the concentration on the resulting self-assembly of TMA molecules at the LSI is estimated by another experiment using stirring (from 0 h to 40 h) of the solutions of different kinds of solvents. These results demonstrate that choosing different preparation methods (increasing deposition temperatures or stirring) lead to the same tendency in the change of the self-assembled structures as well as the tuning of the packing density from which it can also be concluded that the increase of the concentration at increased deposition temperatures is also the main reason for the observed changes. The second focus of this work is the investigation of chemical reactions of self-assembling molecules. The esterification of TMA with undecanol was observed. Moreover as a first step to study twin polymerization, the oligomerization of the twin monomer 2,2’-spirobi [4H-1,3,2-benzo-dioxasiline] (SBS) was investigated by STM at the SBS-undecanol solution/graphite interface. Firstly, by ultrasonicating the solution of SBS in undecanol for different times the oligomerization of SBS monomer without any catalyst has been observed at the LSI. Secondly, the oligomerization of SBS monomer can also be initiated by the substrate temperature during the deposition of the molecules out of the solution. By stepwise increasing the temperature of the pre-heated substrate, various periodic assemblies of phenolic dimer, trimer, pentamer resin, and so on were observed. Furthermore, the effect of deposition temperature on the self-assembly of solely solvent molecules from the pure liquid at the LSI is described, which is important because the undecanol solvent molecules are always co-adsorbed with the solutes used in this work (TMA, BTP, SBS) to form linear patterns.:Chapter 1: Introduction
Chapter 2: Basic principle
2.1 Principles of scanning tunneling microscopy (STM)
2.1.1 General working principle
2.1.2 Tunneling effect
2.1.3 Theory of STM
2.1.4 Contrast mechanism of molecular adsorbates
2.1.5 Modes of STM operation
2.2 STM at the liquid-solid interface (LSI)
2.3 Thermodynamics and kinetics
2.3.1 Equilibrium of the adsorption/desorption and initial agglomeration at the LSI
2.3.2 Kinetic and thermodynamic control over 2D molecular self-assembly
2.4 Experimental condition
2.4.1 Role of solvent
2.4.2 Role of concentration
2.4.3 Role of temperature
References
Chapter 3: Experimental section
3.1 Solutes
3.1.1 Trimesic acid (TMA) (1,3,5?C6H3(COOH)3)
3.1.2 Benzene 1.3.5-Triphosphonic acid (BTP) (1,3,5?C6H3(PO3H2)3)
3.1.3 Twin monomer 2,2’-spirobi[4H-1,3,2-benzo-dioxasiline] (SBS)
3.2 Solvents
3.3 Substrate: Highly oriented pyrolytic graphite (HOPG (0001))
3.4 Preparation of the STM tips
3.5 Experimental methods for sample preparation
3.5.1 Preparation of the solution
3.5.2 Heating of the substrate
3.5.3 Ultrasonication
3.5.4 Stirring
3.6 Computational details
References
Chapter 4: Deposition temperature? and solvent-dependent 2D supramolecular assemblies of trimesic acid at the liquid-graphite interface revealed by STM
Results and discussion
4.1 Hydrogen bonding motifs of trimesic acid molecules
4.2 TMA deposited from solution in octanoic acid
4.3 TMA deposited from solution in phenyloctane
4.4 TMA deposited from solution in undecanol
4.6 Discussion of the solute–solvent interactions
4.5 Effect of the deposition substrate temperature on the formation of ester at the LSI of TMA in undecanol
Conclusion
References
Chapter 5: Role of concentration on the self-assembly of TMA at the LSI influenced by stirring time
Results and discussion
5.1 TMA in octanoic acid
5.2 TMA in phenyloctane
5.3 TMA in undecanol
Conclusion
References
Chapter 6: Role of deposition temperature on the self-assembly of the non-planar molecule benzene- 1,3,5- triphosphonic acid (BTP) at the LSI
Results and discussion
6.1 BTP in undecanol at room temperature
6.2 BTP in undecanol at high substrate temperature during deposition
Conclusion
References
Chapter 7: Role of deposition temperature on the self-assembly of pure undecanol solvent at the LSI
Results and discussion
7.1 Adsorption geometry of undecanol on HOPG
7.2 Herringbone structures of undecanol
7.3 Parallel structure of undecanol at high substrate temperature during deposition
Conclusion
References
Chapter 8: A first step to microscopically study twinpolymerization: self-assembly of twin monomer 2,2’-Spirobi[4H-1,3,2-benzo-dioxasiline] (SBS) at the LSI influenced by ultrasonication and deposition substrate temperature
8.1 Coadsorption of SBS and undecanol without ultrasonication and at room temperature
8.2 SBS deposited from solution in undecanol in dependence on the duration of ultrasonication
8.3 SBS deposited from solution in undecanol
at varied deposition temperature of the substrate
8.4 Discussion and open questions
Appendix
References
CHAPTER 9: SUMMARY AND OUTLOOK
ERKLÄRUNG
CURRICULUM VITAE
ACKNOWLEDGEMENT
| Identifer | oai:union.ndltd.org:DRESDEN/oai:qucosa:de:qucosa:20684 |
| Date | 17 January 2017 |
| Creators | Nguyen, Doan Chau Yen |
| Contributors | Hietschold, Michael, Deibel, Carsten, Technische Universität Chemnitz |
| Source Sets | Hochschulschriftenserver (HSSS) der SLUB Dresden |
| Language | English |
| Detected Language | English |
| Type | doc-type:doctoralThesis, info:eu-repo/semantics/doctoralThesis, doc-type:Text |
| Rights | info:eu-repo/semantics/openAccess |
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