Au cours de cette thèse, nous avons synthétisé et caractérisé de nouveaux composés en utilisant le macrocycle porphyrinique comme brique moléculaire de départ. Le but de ce travail étant l’étude des propriétés optiques de ces nouveaux composés obtenus. Après avoir effectué l’étude bibliographique sur les porphyrines, nous avons fait une présentation générale des porphyrines symétriques et non symétriques, de leurs propriétés et de leurs synthèses. D’autre part, nous avons aussi considéré l’unité fluorène qui possède des propriétés photophysiques très intéressantes comme antenne collectrice de lumière. Puis, nous avons abordé des méthodes de synthèse permettant d’associer le macrocycle porphyrinique avec de nombreuses unités fluorènes. Cette association a pu être réalisée de différentes manières : soit de façon dendritique ou par connexion directe sur la porphyrine (dimère et trimère). Nous avons également décrit l’obtention d’une nouvelle famille de porphyrines substituées par des groupements organométalliques de type acétylure de ruthénium et de fer pour l’optique non linéaire de troisième ordre (ONL TO). Lors de la dernière partie de mes travaux de thèse, comme application de ces composés luminescents dans le rouge, nous avons reporté l’élaboration de différents dispositifs de diodes électroluminescentes (OLED) émettant dans le rouge. / During this thesis, we have worked on the synthesis and characterization of new compounds using the porphyrin macrocycle as a starting material. The aim, after synthesis, is to study the photophysical properties of these new molecules. A general bibliographic study was presented followed by introducing the synthetic methods of porphyrins and characterization means. Then, fluorene was considered to be an attracting unit due to its interesting photophysical properties: acting as efficient antennae for collecting light. First, we have presented the synthesis of porphyrin dendrimers having fluorenyl arms of different generations. That is to test the effect of number of fluorenes on the photophysical properties. Another way is to connect the fluorenes directly to the porphyrin core by synthesizing porphyrin dimer and trimer. We have also detailed the synthesis and characterization of a new family of porphyrin organometallic assemblies possessing ruthenium and iron moieties. In addition, a new organometallic porphyrin dendrimer bearing twelve ruthenium species was reported as well. These organometallic porphyrins are of interest in the third order of Nonlinear Optics (NLO). In the last chapter of this thesis we showed an example of application of porphyrin chemistry. We reported the elaboration of a new organic light emitting Diode (OLED) using these new porphyrins that emits in the red region.

In this study, conjugated monomers containing fluorene units / 2-(9,9-dihexyl-2-(thiophen-2-yl)-9H-fluoren-7-yl)thiophene (TFT) and 5-(9,9-dihexyl-2-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-9H-fluoren-7-yl)-2,3dihydrothieno[3,4b ][1,4] dioxine (EFE) were synthesized on the basis of donor-acceptor-donor approach and their electrochemical polymerization were achieved via potential cycling. Optical and electrochemical properties of their corresponding polymers, poly(2-(9,9-dihexyl-2-(thiophen-2-yl)-9H-fluoren-7-yl)thiophene) PTFT, and poly(5-(9,9-dihexyl-2-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-9H-fluoren-7-yl)-2,3dihydrothieno[3,4b ][1,4] dioxine) PEFE, were investigated and it was found that polymer films exhibited quasi-reversible redox behavior (Epox= 1.10 V for PTFT, Epox = 0.70 V and 1.00 V for PEFE) accompanied with a reversible electrochromic behavior, yellow to dark green for PTFT, yellow to parliament blue for PEFE. Their band gap values (Eg) were found to be 2.36 eV and 2.26 eV for PTFT and PEFE, respectively. Furthermore, gold nanoparticles (AuNP) were prepared and their interaction with polymer films, PTFT and PEFE, were investigated using spectroscopic techniques. The fluorescence properties of the polymers and their composites, prepared by the interaction of AuNP with polymers, were also investigated.

2-Dodecyl benzotriazole and 9,9-dioctylfluorene containing alternating copolymers poly((9,9-dioctylfluorene)-2,7-diyl-(2-dodecyl-benzo[1,2,3]triazole)) (P1), poly((9,9-dioc-tylfluorene)-2,7-diyl-(4,7-bis(thien-2-yl) 2-dodecyl benzo[1,2,3]triazole)) (P2), poly((9,9 dioctylfluorene)-2,7-diyl-(4,7-bis(3-hexylthien-5-yl) 2-dodecyl-benzo[1,2,3]triazole)) (P3) were synthesized via Suzuki polycondensation. Synthesized monomers and copolymers were characterized by Nuclear Magnetic Resonance (1H-NMR, 13C-NMR). Optical and electronic properties of resulting alternating copolymers were investigated by means of Cyclic Voltammetry (CV), Ultraviolet&ndash / Visible Spectroscopy and spectroelectrochemistry. All three polymers showed both p and n doping behaviors and multicolored electrochromic states. In order to learn switchingtimes and percent transmittance changes kinetic studies were also performed. Thermal properties of the polymers were investigated via Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC). Due to the convenient HOMO and LUMO levels, band gaps, strong absorptions in the visible region and thermal stability, polymers were tested in Organic Solar Cell (OSC) device applications. The preliminary investigation indicated that polymers had promising power conversion efficiencies.

In this study, a novel series of conjugated monomers containing furan and fluorene units / 2,7-di(furan-2-yl)-9H-fluoren-9-one (FOF), 2-(2-(furan-2-yl)-9H-fluoren-7-yl)furan (FFF), and 2-(2-(furan-2-yl)-9,9-dihexyl-9H-fluoren-7-yl)furan (FHF) were synthesized and their electrochemical polymerization were achieved via potential cycling. Optical and electrochemical properties of the polymers, poly(2,7-di(furan-2-yl)-9H-fluoren-9-one) (PFOF), poly(2-(2-(furan-2-yl)-9H-fluoren-7-yl)furan (PFFF) and poly(2-(2-(furan-2-yl)-9,9-dihexyl-9H-fluoren-7-yl)furan) (PFHF) were investigated and it was found that polymer films exhibit reversible redox behavior (Epox = 1.083 V for PFOF, Epox= 0.915 V for PFFF and Epox= 0.985 V for PFHF) accompanied with a reversible electrochromic behavior, orange to green for PFOF, yellow to dark blue for PFFF and orange to green for PFHF during oxidation. Their band gap values (Eg) were found to be 2.32, 2.49 and 2.61 eV for PFOF, PFFF and PFHF, respectively.

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The gas-phase ion chemistry of hydroxyl- and amino-substituted polycyclic aromatic hydrocarbons (PAHs) and their protonated counterparts were studied using mass spectrometry. Ions were generated using an electron ionization (EI) source and the unimolecular chemistry of metastable ions was studied by performing mass-analysed ion kinetic energy spectrometry (MIKES) experiments with a magnetic sector tandem mass spectrometer. Collision-induced dissociation (CID) experiments were used in conjunction with MIKES experiments to determine ion structure. The ten molecules studied were: 1-naphthol, 2-naphthol, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, 1-phenanthrol, 9-phenanthrol, 1-hydroxypyrene and 1-aminopyrene. Since it is believed that larger PAHs, on the order of more than 50 carbon atoms, populate the interstellar medium, the goal of this study was to attempt to extrapolate the results from smaller systems to larger ones. The trends found include: hydroxy-substituted PAH radical cations lose carbon monoxide spontaneously and amino-substituted PAH radical cations lose HCN. Mechanisms for both processes are proposed, and it appears from the present results that this process should extrapolate to larger PAHs. Another trend found was that all the remaining fragment ions were always a closed ring. Protonated amino-substituted PAHs were generated by electrospray ionization using a quadruple time-of-flight mass spectrometer. By protonating 1-naphthol and 2-naphthol using methane in the high-pressure EI source, it was found that they lost exclusively H2O. As for 2-naphthylamine, 1-aminoanthracene and 2-aminoanthracene, it was found that 2-naphthylamine lost NH3 and a hydrogen atom, NH3being the dominant channel. However, as the ion size 3 increases, the hydrogen-loss channel became the dominant channel. This means that larger PAHs will likely lose exclusively a hydrogen atom to reform the parent radical cation.

This work is divided into two parts that are focused on the synthesis and assessment of photophysical properties of two structurally related compounds: (i) 9,9'-spirobifluorenes (SBFs) and (ii) dispiroindeno[2,1-c]fluorenes (DS-IFs). (i) In the first part, a five-step synthetic approach to SBFs was developed and as the crucial step was used an intermolecular [2+2+2] cyclotrimerization of symmetrically or unsymmetrically substituted diynols with alkynes catalyzed by Rh-complexes. Catalyst screening showed that Wilkinson's catalyst (RhCl(PPh3)3) had the highest efficiency in yielding 1,2,3,4-substituted fluorenols - the key intermediates. The fluorenols were then converted into SBFs bearing various electron-donating and -withdrawing groups, aromatic substituents, and -extended aromatic hydrocarbon moieties (PAHs). Altogether 19 different SBFs were prepared and their photophysical properties screened. The fluorescent emission maxima em were in the range of 315-389 nm with excellent quantum yields s (up to 1.00). As far as the substituent effect is concerned the presence of electron-withdrawing substituents on the SBF scaffold results in the red-shift of the emission maxima. (ii) In the second part, a similar synthetic strategy was applied for synthesis DS-IFs. In this instance was utilized again the...

Three-dimensional (3D) optical data storage based on two-photon processes provides highly confined excitation in a recording medium and a mechanism for writing and reading data with less cross talk between multiple memory layers, due to the quadratic dependence of two photon absorption (2PA) on the incident light intensity. The capacity for highly confined excitation and intrinsic 3D resolution affords immense information storage capacity (up to 1012 bits/cm3). Recently, the use of photochromic materials for 3D memory has received intense interest because of several major advantages over current optical systems, including their erasable/rewritable capability, high resolution, and high sensitivity. This work demonstrates a novel two-photon 3D optical storage system based on the modulation of the fluorescence emission of a highly efficient two-photon absorbing fluorescent dye (fluorene derivative) and a photochromic compound (diarylethene). The feasibility of using efficient intermolecular Förster Resonance Energy Transfer (RET) from the non-covalently linked two-photon absorbing fluorescent fluorene derivative to the photochromic diarylethene as a novel read-out method in a two-photon optical data storage system was explored. For the purpose of the development of this novel two-photon 3D optical storage system, linear and two-photon spectroscopic characterization of commercial diarylethenes in solution and in a polymer film and evidence of their cyclization (O→C) and cycloreversion (C→O) reactions induced by two-photon excitation were undertaken. For the development of a readout method, Resonance Energy Transfer (RET) from twophoton absorbing fluorene derivatives to photochromic compounds was investigated under one and two-photon excitation. The Förster's distances and critical acceptor concentrations were determined for non-bound donor-acceptor pairs in homogeneous molecular ensembles. To the best of my knowledge, modulation of the two-photon fluorescence emission of a dye by a photochromic diarylethene has not been reported as a mechanism to read the recorded information in a 3D optical data storage system. This system was demonstrated to be highly stable and suitable for recording data in thick storage media. The proposed RET-based readout method proved to be non-destructive (exhibiting a loss of the initial fluorescence emission less than 20% of the initial emission after 10,000 readout cycles). Potential application of this system in a rewritable-erasable optical data storage system was proved. As part of the strategy for the development of diarylethenes optimized for 3D optical data storage, derivatives containing Ï€-conjugated fluorene molecules were synthesized and characterized. The final part of this reasearch demonstrated the photostability of fluorine derivatives showing strong molecular polarizability and high fluorescence quantum yields. These compounds are quite promising for application in RET-based two-photon 3D optical data storage. Hence, the photostability of these fluorene derivatives is a key parameter to establish, and facilitates their full utility in critical applications.

The diploma thesis presents the preparation of ,-bisterpyridinylfluorenes (unimers) containing fluorene unit in the central block either directly attached to terpyridine (tpy) end groups or via 1,4-phenylene or thiophene-2,5-diyl linker. Synthesized unimers were subsequently used for the preparation of metallo-supramolecular polymers with Zn2+ and Fe2+ ions. The prepared unimers were characterized by NMR, IR and HR-MS, their optical properties were investigated using absorption and emission spectroscopy and cyclic voltammetry. Molecular weight distribution for the prepared Fe-polymers was determined by GPC. The number-average degree of polymerization equal to 7 for an equimolar ratio between unimer and Fe2+ in a diluted solution was determined for polymers composed of unimer with thiophene-2,5- diyl linker. By using the viscometric measurements the ongoing constitutional dynamics in solutions of metallo-supramolecular polymers was proven. The overstoichiometric amount of metal ions in solution resulted in equilibrium shortening of the polymer chains together with end-capping of terminal tpy ligands by Mt2+ ions. Unimer with thiophene-2,5-diyl linker exhibited unique properties involving significantly red-shifted absorption and emission maxima, as well as the different behavior during assembling...