The investigation and control of the properties of carbon based materials such as fullerenes
and nanotubes is a highly dynamic research field. Due to its unique properties, e.g. an almost nano-dimensional size, three-dimensional cage topology, hydrophobicity, rich redox- and photochemistry, large absorption cross section, C60 has a high potential as building block for molecular devices and biological applications. It can be functionalized, anchored to a surface and self-assembled into larger supramolecular entities, such as monolayers. Mass
spectrometry and related techniques such as ion-molecule reactions, action spectroscopy and ion mobility have been used throughout this work to study fullerene based systems, ranging from hydrides, derivatives, non-covalent complexes and coordinated metal complexes.
Simulations predicting structural, electronic and mechanical properties have been combined with the experimental results to assist in their analysis and interpretation. Using ion molecule reactions, the reactivity of gas phase C60 anions with methanol has been studied. Hydride formation by simple collisions in the gas phase with methanol as well as reversible
dehydrogenation by infrared multiphoton activation has been demonstrated. C60
functionalization by 3-azido-3-deoxythymidine (AZT) has been performed and the charged product characterized both by collisional activation and action spectroscopy. Deprotonation has been shown to lead to rearrangements of the nucleoside analogue and to a subsequent charge transfer to the fullerene. To prevent unwanted rearrangements and side reactions,
encapsulation of C60 is suggested, the host molecule acting as a steric barrier.
C60 complexation by γ-cyclodextrins has been performed and the ions of the complexes characterized both by collisional activation and ion mobility. It has been demonstrated that,
compared to deprotonated species, the sodiated C60:(γ-cyclodextrin)2 ions were highly compact structures.
With only two small polar caps accessible to reagents, sodiated C60:
(γ-cyclodextrin)2 complexes sterically protect the C60 core from unwanted side reactions.
Finally, explorative work on C60 immobilization on silver colloids using surface enhanced Raman spectroscopy and on the characterization of C60 complexes with iron and manganese
porphyrin is presented.
| Identifer | oai:union.ndltd.org:BICfB/oai:ETDULg:ULgetd-04082009-092228 |
| Date | 27 October 2008 |
| Creators | Greisch, Jean-François |
| Contributors | ZENOBI, Renato, DE PAUW, Edwin, MARIEN, José, PIRARD, Jean-Paul, Crine, Michel, CAMPBELL, Eleanor E. B., DREWELLO, Thomas, LEYH, Bernard |
| Publisher | Universite de Liege |
| Source Sets | Bibliothèque interuniversitaire de la Communauté française de Belgique |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://bictel.ulg.ac.be/ETD-db/collection/available/ULgetd-04082009-092228/ |
| Rights | unrestricted, Le contrat BICTEL/e complété et signé a été remis au gestionnaire facultaire. |
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