No description available.

L'avènement de terminaux avancés permet l'accès à des services toujours plus gourmands en bande passante, avec notamment le déploiement de services de vidéo mobile sans couture offert par le mode diffusion mobile intégré standardisé par le 3GPP. Dans le même temps, la communauté << broadcast » s'est adaptée aux nouveaux usages de télévision mobile avec la norme DVB-NGH (Digital Video Broadcasting - Next Generation Handheld). Dans ce contexte, l'objectif de cette thèse est d'étudier la convergence spectrale entre les deux réseaux DVB et LTE en déployant une petite cellule LTE au sein d'une grande cellule DVB. Les deux technologies utilisent une forme d'onde OFDM (Orthogonal Frequency Division Multiplexing), en liaison descendante pour le LTE, ct possèdent donc quelques similarités tout en étant assez différentes par leurs caractéristiques. Dans ces travaux, nous nous intéressons aux performances atteignables lorsque les deux systèmes se recouvrent spectralement sans coopération. Le problème considéré étant analogue à un problème d’utilisateur secondaire opérant en mode recouvrement avec un utilisateur primaire, on commence par étudier le problème de la capacité ergodique du système secondaire, i.e. utilisateur LTE, sous contraintes de puissance moyenne générée par le secondaire sur le primaire, i.e LTE sur DVB, et de puissance crête au secondaire lorsque l'utilisateur primaire interfère sur le secondaire. Le problème est résolu analytiquement dans le cas général du canal croisé avec évanouissements de Rayleigh. Dans un deuxième temps nous étendons cette étude préliminaire au cas où la forme d'onde des deux systèmes primaire et secondaire est effectivement de type OFDM. En considérant d'abord un modèle simple de recouvrement total des sous-porteuses, nous délivrons la capacité ergodique globale ce qui nous permet d'évaluer l'influence des paramètres des systèmes, comme le nombre de sous-porteuses de chaque système ou les puissances interférentes, sur les capacités globales et individuelles. Nous nous intéressons ensuite à l'optimisation de la capacité globale où deux stratégies sont étudiées. D'une part, la capacité globale étant la somme de deux fonctions convexe et concave respectivement, la solution obtenue conduit au minimum de capacité globale mais mène à une situation d'équilibre entre les systèmes DVB et LTE. D'autre part, la maximisation de la capacité globale sous contrainte conduit à favoriser largement un système sur l'autre. Enfin, une étude fine de l'interférence causée par un système sur l'autre par recouvrement partiel est menée. L'effet de la variation du taux de recouvrement spectral entre les bandes du DVB et du LTE sur l'efficacité spectrale globale est étudié. On suppose ensuite que le récepteur possède une capacité de réjection de l'interférence permettant de déterminer le recouvrement optimal maximisant la capacité globale. Les différentes contributions de ces travaux ont permis d'avoir une approche théorique sur la modalité d'allocation de puissance des deux systèmes DVB et LTE co-existants et sur le taux de recouvrement approprié entre leurs spectres respectifs. Cette étude pourrait être ut le pour les opérateurs intéressés par un scénario de déploiement dense afin de choisir les configurations optimales des ressources dans une perspective de réutilisation agressive des fréquences. / Since the launch of the first numerical mobile telecommunications networks in the nineties, the quantity of the transmitted data over the networks is increasing year by year. Advanced user equipments enable to implement more and more bandwidth consuming services such as mobile T and multimedia internet, available in the integreted mobile broadcast mode recently standardized by the 3GPP group. In the meanwhile, the digital vide broadcasting - next generation handled (DVB-NGH) has been released in order to satisfy the increasing demand for mobile TV. These technologies compete for a more and more constrained spectral resource leading to question the possibility to deploy DVB and Long Term Evolution (LTE) service in a spectral overlay mode as it has been investigated by the Ml project funded by the National Research Agency. In this context, this thesis aims at studying the spectral convergence between DVB and LTE networks by deploying a small LTE cell in a large DVB cell. Both technologies present some similarities, i.e. both use orthogonal frequency division multiplexing (OFDM) waveform (in downlink for LTE), but technical characteristics remain rather different between those. In this work, we deal with achievable performance when DVB and LTE spectrally overlap without cooperation. The considered problem being analog to the Seconda1y User (SU) - Primary User (PU) coexistence in overlay scenario, the SU ergodic capacity under average power generated on PU and peak power at SU constaints is investigated. An analytic solution is proposed in X-Channel with Rayleigh fading. In a second time, SU and PU are considered to be LTE and DVB respectively with their particular OFDM signal characteristics. With a first model of overlapping subcarriers, LTE and DVB ergodic capacities and global capacity as well are derived in closed form allowing to study the influence of several system parameters on ergodic capacities. The global capacity is then optimized using a convex-concave procedure leading to the minimum on the global capacity but to balanced capacity on individual links. On a second hand, global capacity maximization leads to favor one system over the other. Last but not least, a careful study of the interference caused by one system over the other by partial overlay is led. The effect of spectral overlap ratio between DVB and LTE systems over the global spectral efficiency is investigated. Advanced interference rejection ability is then assumed at receivers and the optimal spectral overlap, i.e. maximizing the global capacity, is then derived in that case. The different contributions in this work give a theoretical approach on the power allocation modality of two coexisting DVB and LTE systems and on the appropriate spectral overlap ratio between their respective spectrums. This study can be useful for operators interested in dense network deployment scenarios to decide the operating point of allocated resources in a very aggressive frequency reuse pattern.

A key component of natural photosynthesis are the antenna chromophores (chlorophylls and carotenoids) that capture solar energy and direct it towards the reaction centers of photosystems I and II. Highlighted by highly-ordered crystal structures and synthetic tunability via crystal engineering, metal–organic frameworks (MOFs) have the potential to mimic the natural photosynthetic systems in terms of the efficiency and directionality of energy transfer. Owing to their larger surface areas, MOFs have large absorption cross sections, which amplifies the rate of photon collection. Furthermore, MOFs can be constructed using analogues of chlorophyll and carotenoids that can participate in long-range energy transfer. Herein, we aimed to design photoactive MOFs that can execute one of the critical steps involved in photosynthesis - photon collection and subsequent energy transfer. The influence of spatial arrangement of chromophores on the efficiency and directionality of excitation energy transfer (EET) was investigated in a series of mixed-ligand pyrene- and porphyrin-based MOFs. Due to the significant overlap between the emission spectrum of 1,3,6,8-tetrakis(p-benzoic acid)pyrene (TBAPy) and the absorption spectrum of meso-tetrakis(4-carboxyphenyl)porphyrin (TCPP), the co-assembly of these two ligands in a MOF should enable facile energy transfer. Bearing this in mind, three TBAPy-based MOFs with markedly different network topologies (ROD-7, NU-901, and NU-1000) were chosen and a small number of TCPP units were incorporated in their backbone. To gain insight into the photophysical properties of mixed-ligand MOFs, we conducted time-resolved and steady-state fluorescence measurements on them. Stern-Volmer analysis was performed on the fluorescence lifetime data of mixed-ligand MOFs to determine the quenching constants. The quenching constant values for ROD-7, NU-901, NU-1000, and TBAPy solution were found to be 15.03 ± 0.82 M-1, 10.25 ± 0.99 M-1, 8.16 ± 0.41 M-1, and 3.35 ± 0.30 respectively. In addition, the ratio of the fluorescence intensities of TCPP and TBAPy was used to calculate the EET efficiencies in each of the three MOFs. EET efficiencies were in the following order: ROD-7 > NU-901 > NU-1000 > TBAPy-solution. Based on the trends observed for quenching constants and EET efficiencies, two conclusions were drawn: (1) the ligand-to-ligand energy transfer mechanism in MOFs outperforms the diffusion-controlled mechanism in solution phase, (2) energy transfer in MOFs is influenced by their structural parameters and spectral overlap integrals. The enhanced EET efficiency in ROD-7 is attributed to shorter interchromophoric distance, larger orientation factor, and larger spectral overlap integral. Directionality of energy transfer in these MOFs was assessed by calculating excitonic couplings between neighboring TBAPy linkers using the atomic transition charges approach. Rate constants of EET (kEET) along different directions were determined from the excitonic couplings. Based on the kEET values, ROD-7 is expected to demonstrate highly anisotropic EET along the stacking direction. In order to explore the mechanistic aspects of EET in porphyrin-based MOFs, we studied the energy transfer characteristics of PCN-223, a zirconium-based MOF containing TCPP ligands. After performing structural characterization, the photophysical properties of PCN-223 and free TCPP were investigated using steady state and time-resolved spectroscopy. pH-dependent fluorescence quenching experiments were performed on both the MOF and ligand. Stern-Volmer analysis of quenching data revealed that the quenching rate constants for PCN-223 and TCPP were 8.06 ± 1011 M-1s-1 and 2.71 ± 1010 M-1s-1 respectively. The quenching rate constant for PCN-223 is, therefore, an order of magnitude larger than that for TCPP. Additionally, PCN-223 demonstrated a substantially higher extent of quenching (q = 93%) as compared to free TCPP solution (q = 51%), at similar concentrations of quencher. The higher extent of quenching in MOF is attributed to energy transfer from neutral TCPP linkers to N-protonated TCPP linkers. Using the Förster energy transfer model, the rate constant of EET in PCN-223 was calculated. The magnitude of rate constant was in good agreement with the kEET values reported for other porphyrin-based MOFs. Nanosecond transient absorption measurements on PCN-223 revealed the presence of a long-lived triplet state (extending beyond 200 μs) that exhibits the characteristic features of a TCPP-based triplet state. The lifetime of MOF is shorter than that of free ligand, which may be attributed to triplet-triplet energy transfer in the MOF. Lastly, femtosecond transient absorption spectroscopy was employed to study the ultrafast photophysical processes taking place in TCPP and PCN-223. Kinetic analysis of the femtosecond transient absorption data of TCPP and PCN-223 showed the presence of three distinct time components that correspond to: (a) solvent-induced vibrational reorganization of excitation energy, (b) vibrational cooling, and (c) fluorescence. Materials that allow control over the directionality of energy transfer are highly desirable. Core-shell nanocomposites have recently emerged as promising candidates for achieving long-distance, directional energy transfer. For our project, we aim to employ UiO-67-on-PCN‐222 composites as model systems to explore the possibility of achieving directional energy transfer in MOF-based core-shell structures. The core–shell composites were synthesized by following a previously published procedure. Appropriate amounts of Ruthenium(II) tris(5,5′-dicarboxy-2,2′-bipyridine), RuDCBPY, were doped in the shell layer to produce a series of Ru-UiO-67-on-PCN‐222 composites with varying RuDCBPY loadings (CS-1, CS-2, and CS-3). The RuDCBPY-doped core–shell composites were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) imaging, Nitrogen adsorption-desorption isotherms, and diffuse reflectance spectroscopy. Efforts are currently underway to quantify RuDCBPY loadings in CS-1, CS-2, and CS-3. After completing structural characterization, the photophysical properties of CS-1, CS-2, and CS-3 will be investigated with the help of time-resolved and steady-state fluorescence spectroscopy. / Doctor of Philosophy / The pigment−protein complexes in natural photosynthetic units (also known as light harvesting antennas) efficiently capture solar energy and transfer this energy to reaction centers that carry out water splitting reactions. The collective chromophoric behavior of antennas can be replicated by metal-organic frameworks (MOFs). MOFs are crystalline, self-assembled materials composed of metal clusters connected by organic molecules. In this dissertation, we study the factors that govern the energy transfer and light harvesting capabilities of MOFs. In chapter 2, we examined the role of 3D structure of MOFs in energy transfer. In chapter 3, we investigated the influence of pH and temperature on the photophysical properties of MOFs. In chapter 4, we explored the possibility of energy transfer in novel MOF-on-MOF composites. This work is intended to pave the way for the construction of highly efficient MOF-based materials that can serve as the light harvesting and energy-transfer components in solar energy conversion devices.