The D-A and π-π Interactions and Their Use in Self-Assembly Due to their well-defined shape, size and properties gold nanoparticles represent an advantageous platform for the study of non-covalent interactions between ligands anchored to their surface both in solution and in monolayers or thin films. The aim of this thesis was the synthesis of ligands for gold nanoparticles bearing an anchoring group at one end and a planar π-electron rich pyrene unit at the other. Six structurally variable ligands were prepared differing in the pyrene substitution pattern and the spacer between the aromatic part and the acetylated thiol function. Furthermore, a synthetic pathway leading to extended π-electron systems (both electron rich and electron poor) such as hexabenzocoronene derivatives and its fragments was explored. The key steps in the synthesis of these compounds are the cyclization reactions of alkynes leading to polycyclic intermediates and their ensuing cyclodehydrogenation (Scholl reaction). All of the prepared ligands and their intermediates were characterized by spectroscopic methods. The structure of the key hexakis(pentafluorosulfanyl-phenyl)benzene was confirmed by single crystal X-ray crystallography. The prepared ligands bearing a pyrene unit were deacetylated and anchored to the surface of...

Ce travail de recherche prédictive, couplé à des synthèses expérimentales, a pour but d'anticiper la bonne adéquation entre un nouveau polymère donneur de type P3HT et un composé accepteur innovant à base de graphène. Cette étude a notamment porté sur i) la bande d'absorption du polymère donneur « low band gap », ii) sa robustesse face à la dégradation (cristallinité, résistance à l'oxydation), iii) la modulation des propriétés électroniques d'un dérivé de graphène (accepteur) en adéquation avec le donneur. Les résultats montrent que les polythiophènes ayant un substituant éther OR permettent l'amélioration de la conjugaison, de la rigidité, de la cristallinité et de la photostabilité tout en étant électroniquement compatible avec l'hexabenzocoronène fonctionnalisé (acide caorboxylique). De plus, ce nouvel accepteur sera pleinement compatible avec une électrode de graphite grâce à sa prédisposition à l'empilement colonnaire. / This predictive research work, combined with an experimental study, aims at anticipate the behavior of a new donor :acceptor pair constituted by a P3HT-type of polymer and an innovative graphene-based acceptor material (HBC). This study is particularly interested in i) the absorption band of the donor (a « low band gap » polymer) and ii) its resistance towards degradation (cristallinity, oxidation stability), and finally iii) the modulation of the electronic properties of the acceptor, in keeping with those of the donor. Results show that polythiophenes grafted with an –OR group improve both conjugation, rigidity, cristallinity and photostability, in addition to their great electronic compatibility with functionalized HBCs. Besides, this new acceptor material will be fully compatible with a graphite electrode, thanks to its columnar structuration.

Herein, we report on the mechanochemical Scholl reaction of dendritic oligophenylene precursors to produce benchmark nanographenes such as hexa-peri-hexabenzocoronene (HBC), triangular shaped C60 and expanded C222 under solvent-free conditions. The solvent-free approach overcomes the bottleneck of solubility limitation in this well-known and powerful reaction. The mechanochemical approach allows tracking the reaction process by in situ pressure measurements. The quality of produced nanographenes has been confirmed by MALDI-TOF mass spectrometry and UV-Vis absorption spectroscopy. This approach paves the way towards gram scale and environmentally benign synthesis of extended nanographenes and possibly graphene nanoribbons suitable for application in carbon based electronics or energy applications.

Im ersten Teil der Arbeit werden Graphen sowie von Monolagen von auf Nanometer großen Graphenen basierenden Hexa-peri(Dodekyl)-Hexabenzocoronen-Molekülen (HBC-C12), adsorbiert auf Graphen, mit Rastertunnelmikroskopie und –spektroskopie an der Fest-Flüssig-Grenzfläche untersucht. Nanographen-Moleküle selbstaggregieren epitaktisch zu hochgeordneten Monolagen. Die Einheitszellen der Moleküllagen auf Monolage Graphen, Bilage Graphen und auf Graphit sind ununterscheidbar. Die Strukturen der Moleküllagen auf gewellten und flachen Teilen des Graphens stimmen überein. Strom-Spannungs-Kennlinien an Nanographen auf Graphen und auf Graphit weisen auf sehr ähnliche elektronische Eigenschaften hin. Zusammengefasst sind strukturelle sowie elektronische Eigenschaften der Nanographenlage homogen, stabil und definiert. Graphen erweist sich als bestens als Substrat und gleichzeitig als Elektrode für hochgeordnete Lagen von Nanographen-Molekülen geeignet. Im zweiten Teil der Arbeit wird Graphen mit der Sonde eines Rasterkraftmikroskops im Kontaktmodus mechanisch manipuliert. Es wird gezeigt, dass Graphen in nur einem Manipulationsschritt zu Streifen und Spalt geschnitten werden kann. Dieses Verhalten wird mit einem klassischen Modell des Biegens theoretisch erklärt. Das Schnittverhalten liegt in der 2-Dimensionalität des Graphens sowie in dessen Faltbarkeit auf Grund hinreichender Elastizität begründet. Durch mechanische Manipulation mit der Sonde des Rasterkraftmikroskops im Kontaktmodus unter atmosphärischen Bedingungen wird eine Flüssigkeitsschicht zwischen Graphen und dem Siliziumdioxidsubstrat nachgewiesen, welche eine mögliche Erklärung des stark kraftabhängigen Materialkontrasts zwischen Graphen und Siliziumdioxid im Amplitudenmodulationsmodus des Rasterkraftmikroskops darstellt. Weiter wird gezeigt, dass das Falten des Graphens durch mechanische Manipulation eine geeignete Methode zur Herstellung nicht epitaktisch aufeinander gestapelter Graphene darstellt. / In the first part of the thesis graphene as well as monolayers of hexa-peri(dodecyl)-hexabenzocoronene molecules (HBC-C12) based on nanometer sized graphenes adsorbed on graphene is investigated by scanning tunnelling microscopy and tunneling spectroscopy at the solid-liquid interface. The nanographene molecules self-assemble on graphene epitaxially to form highly ordered monolayers. The unit cells of the molecular layers on monolayer graphene, bilayer graphene and on graphite appear identical. The structures of the molecular layers occur equal on corrugated and on flat parts of graphene. Current-voltage-characteristics show that the electronic properties of nanographene on graphene and on graphite are very similar. Summarized, structural as well as electronic properties of the nanographene layer are homogeneous, stable and defined. Graphene proves to be excellently qualified for simultaneously being substrate as well as electrode for highly ordered layers of nanographene based molecules. In the second part of the thesis graphene is mechanically manipulated in air in contact mode of a scanning force microscope. It is shown that a single manipulation process can lead to a stripe cut out of graphene. This behaviour is theoretically explained by a classical bending model. The cutting behavior originates from the 2-dimensionality of graphene and its folding ability because of sufficient elasticity. A liquid layer between graphene and the silicon dioxide substrate is verified by mechanical manipulation in contact mode of a scanning force microscope. Hence a possible explanation could be found for the strongly force dependent material contrast between graphene and silicon dioxide in amplitude modulation mode of the scanning force microscope. Further, it is demonstrated that folding graphene by mechanical manipulation is a proper method for the production of graphene stacked on each other non-epitaxially.