Reversible Electronic Energy Transfer in Rotaxane Architectures
Description
The focus of this thesis is the establishment and study of reversible electronic energy transfer (REET), following light excitation, between molecular subcomponents within ring-on-thread rotaxane nanometric architectures. When the lowest-lying chromophore excited states are quasi-isoenergetic and kinetics of interchromophore transfer are rapid, REET can be instilled - changing excited-state properties. Pyrene and ruthenium(II) tris(bipyridine) derivatives were chosen as matched chromophores. Rotaxane formation was based on active template copper catalysis (Huisgen and Cadiot-Chodkiewicz reactions) within a pyrene-decorated macrocycle, coupling half threads comprising bulky stopper groups - one of which being Ru(bpy)32+. Prolonged luminescence lifetimes (up to 14 μs), compared to parent Ru(bpy)32+, indicated that reversible electronic energy transfer processes were instilled in a series of rotaxanes of varying structure, which were studied by state-state and time-resolved spectroscopies. (author)
Abstract (French)
L'objectif de cette these est la mise en place et l'etude d'un transfert d'energie electronique reversible (REET), a la suite d'une excitation lumineuse, entre des sous-composants moleculaires au sein d'architectures nanometriques de type rotaxane. Dans un systeme bichromophorique, lorsque les etats excites du chromophore les plus bas sont quasi-isoenergetiques et que la cinetique du transfert interchromophore est rapide, le REET peut etre instille en modifiant les proprietes de l'etat excite. Des derives du pyrene et du tris(bipyridine)ruthenium(II) ont ete choisis comme chromophores apparies. La formation de rotaxane a ete catalysee par du cuivre (reactions de Huisgen et Cadiot-Chodkiewicz) au sein d'un macrocycle dote de pyrene, couplant des demi-fils moleculaires comprenant des groupements terminaux volumineux - dont Ru(bpy)32+. Des durees de vie de luminescence prolongee (jusqu'a 14 μs), comparees au parent Ru(bpy)32+, indiquent que des processus de transfert d'energie electroniques reversibles ont ete etablis dans une serie de rotaxanes de structure variable, sont etudies par spectroscopies stationnaire et resolue dans le temps. (auteur)
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Additional details
Additional titles
- Original title (English)
- Transfert reversible d'energie electronique au sein d'architectures de type rotaxane
Publishing Information
- Imprint Pagination
- 233 p.
- Report number
- FRNC-TH--15014
INIS
- Country of Publication
- France
- Country of Input or Organization
- France
- INIS RN
- 54115717
- Subject category
- S74: ATOMIC AND MOLECULAR PHYSICS; S37: INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY;
- Resource subtype / Literary indicator
- Thesis
- Descriptors DEI
- ABSORPTION SPECTROSCOPY; CATALYSIS; DE-EXCITATION; DENSITY FUNCTIONAL METHOD; ELECTRON TRANSFER; EXCITED STATES; FLUORESCENCE; PHOTOCHEMISTRY; PYRENE; PYRIDINIUM COMPOUNDS; RUTHENIUM COMPLEXES; SYNTHESIS; TITRATION
- Descriptors DEC
- AMMONIUM COMPOUNDS; AROMATICS; AZINES; CALCULATION METHODS; CHEMICAL ANALYSIS; CHEMISTRY; COMPLEXES; EMISSION; ENERGY LEVELS; ENERGY-LEVEL TRANSITIONS; HETEROCYCLIC COMPOUNDS; HYDROCARBONS; LUMINESCENCE; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PHOTON EMISSION; POLYCYCLIC AROMATIC HYDROCARBONS; PYRIDINES; QUANTITATIVE CHEMICAL ANALYSIS; QUATERNARY AMMONIUM COMPOUNDS; SPECTROSCOPY; TRANSITION ELEMENT COMPLEXES; VARIATIONAL METHODS; VOLUMETRIC ANALYSIS
Optional Information
- Notes
- 174 refs.; Available from the INIS Liaison Officer for France, see the INIS website for current contact and E-mail addresses