Synthesis and characterization of multi-porphyrinic scaffolds using NHC linkers

L'objectif de cette thèse a été de mettre au point l'introduction d'azoles en meso d'une porphyrine par couplage d'Ullmann; Divers azoles ont pu être introduit par cette méthode avec de bons rendements, par formation d'une liaison carbone-azote. il a même été possible avec certains azotes de réaliser des doubles couplages d'Ullmann, conduisant ainsi à des 5.15-diazolyle-porphyrines. De plus, ces même conditions réactionnelles ont été utilisées pour introduire un ou deux dérivés donneurs d'électrons (carbazole, phénoxazine, phénothiazine). L'introduction d'imidazole, de triazole et de benzimidazole en meso a permis, après alkylation, d'obtenir des précurseurs de carbènes N-hétérocycles (NHC). La coordination de deux équivalents de NHC sur un sel de palladium conduit à un dimère de porphyrines via coordination exocyclique. La géométrie de coordination trans-anti autour du palladium a été confirmée par l'obtention de la structure radiocristallographique de deux complexes. Les études par électrochimie de ces complexes ont révélé une communication interporphyrinique à l'état fondamental, mise en évidence par une succession de quatre vagues monoélectroniques en oxydation.The purpose of this thesis was to functionalize the meso position of a porphyrinWith azoles using the Ullmann coupling. Various azoles were introduced with good yieldsby using this reaction, leading to the formation of a carbon-nitrogen bond. With someazoles a double Ullmann coupling was possible, resulting in the formation of 5,15-diazolyl-porphyrins. Moreover, the same conditions were used to introduce one ortwo electron-donating groups (carbazole, phenoxazine, phenothiazine). The insertionof imidazole, triazole and benzimidazole at the meso position allowed, afteralkylation, their use as N-heterocyclic carbene (NHC). Coordination of twoequivalents of NHC to a palladium salt led to a porphyrin dimer, as a bis-carbene complex. X-Ray structures revealed that the complex’s geometry was trans-anti. Electrochemistry studies of the various dimers showed interactions between the porphyrins, highlighted by four successive oxidation peaks

Synthèse et caractérisation d'assemblages multi-porphyriniques à espaceurs NHC

The purpose of this thesis was to functionalize the meso position of a porphyrinWith azoles using the Ullmann coupling. Various azoles were introduced with good yieldsby using this reaction, leading to the formation of a carbon-nitrogen bond. With someazoles a double Ullmann coupling was possible, resulting in the formation of 5,15-diazolyl-porphyrins. Moreover, the same conditions were used to introduce one ortwo electron-donating groups (carbazole, phenoxazine, phenothiazine). The insertionof imidazole, triazole and benzimidazole at the meso position allowed, afteralkylation, their use as N-heterocyclic carbene (NHC). Coordination of twoequivalents of NHC to a palladium salt led to a porphyrin dimer, as a bis-carbene complex. X-Ray structures revealed that the complex’s geometry was trans-anti. Electrochemistry studies of the various dimers showed interactions between the porphyrins, highlighted by four successive oxidation peaks.L'objectif de cette thèse a été de mettre au point l'introduction d'azoles en meso d'une porphyrine par couplage d'Ullmann; Divers azoles ont pu être introduit par cette méthode avec de bons rendements, par formation d'une liaison carbone-azote. il a même été possible avec certains azotes de réaliser des doubles couplages d'Ullmann, conduisant ainsi à des 5.15-diazolyle-porphyrines. De plus, ces même conditions réactionnelles ont été utilisées pour introduire un ou deux dérivés donneurs d'électrons (carbazole, phénoxazine, phénothiazine). L'introduction d'imidazole, de triazole et de benzimidazole en meso a permis, après alkylation, d'obtenir des précurseurs de carbènes N-hétérocycles (NHC). La coordination de deux équivalents de NHC sur un sel de palladium conduit à un dimère de porphyrines via coordination exocyclique. La géométrie de coordination trans-anti autour du palladium a été confirmée par l'obtention de la structure radiocristallographique de deux complexes. Les études par électrochimie de ces complexes ont révélé une communication interporphyrinique à l'état fondamental, mise en évidence par une succession de quatre vagues monoélectroniques en oxydation

Physical investigation of the impact of electrolessly deposited self-aligned caps on insulation of copper interconnects

International audienceWith the miniaturization of ULSI circuits and the associated increase of current density up to several MA/cm2, copper interconnects are facing electromigration issues at the top interface with the dielectric capping layer SiC(N). A promising solution is to insert selectively on top of copper lines a CoWP metallic self-aligned encapsulation layer, deposited using a wet electroless process. We study the impact of this process on electrical line insulation as a function of cap thickness at the 65 nm technology node and we investigate the physical origin of leakage currents. Below a critical thickness, only a slight leakage current increase of less than one decade is observed, remaining within the specification for self-aligned capping layer processes. Above this critical thickness, large leakage currents are generated due to the combined effect of lateral growth and the presence of parasitic redeposited nodules. We show that a simple phenomenological model allows to reproduce the experimental data, to assess quantitatively the contribution of parasitic defects, and to predict that the self-aligned barrier technology should be extendible up to the 32 nm node, provided that a thin cap layer of less than 8 nm is used

Porosity evaluation of PoSi wafer using a nondestructive ultrasonic technic

International audienceThe manufacturing processes of porous silicon (PoSi) by electrochemical etching now allow samples with variable depths and variable degrees of porosity to be obtained. However, thickness and porosity measurement methods of PoSi are generally destructive. Therefore in this study a nondestructive ultrasonic method is investigated. For this, an immersion insertion-substitution technique has been used. Samples with different porosities and depths are studied. The thickness of the wafer (550 microns) and high sound speed in pure silicon (8450 m.s-1) require transducers with high central frequencies (from 15 to 50MHz). The acoustic parameters of the wafer, such as velocity and attenuation are measured. These measurements are compared with those obtained through a one-dimensional multilayer model of the wafer, using a homogenisation approach for the porous layer. An inverse method is used to find the PoSi parameters, such as the thickness of the layers or the porosity

Synthesis and Electrochemical Studies of Porphyrin Dimers Linked by Metallocarbenes

The functionalization of porphyrins at the <i>meso</i> positions by azoles led, after subsequent alkylation, to several precursors of N-heterocyclic carbenes. Porphyrin dimers linked by palladium (or rhodium) bis-carbene spacers were prepared and characterized. Spectroscopic data and X-ray structures showed that the coordination geometry for the two carbenes around the palladium linker was <i>trans-anti</i>. Electrochemical studies revealed significant electronic communication between the two porphyrins, despite the absence of conjugation pathways

Synthesis and Electrochemical Studies of Porphyrin Dimers Linked by Metallocarbenes

The functionalization of porphyrins at the <i>meso</i> positions by azoles led, after subsequent alkylation, to several precursors of N-heterocyclic carbenes. Porphyrin dimers linked by palladium (or rhodium) bis-carbene spacers were prepared and characterized. Spectroscopic data and X-ray structures showed that the coordination geometry for the two carbenes around the palladium linker was <i>trans-anti</i>. Electrochemical studies revealed significant electronic communication between the two porphyrins, despite the absence of conjugation pathways

Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors

A series of nickel(II) porphyrins bearing one or two bulky nitrogen donors at the meso positions were prepared by using Ullmann methodology or more classical Buchwald–Hartwig amination reactions to create the new C-N bonds. For several new compounds, single crystals were obtained, and the X-ray structures were solved. The electrochemical data of these compounds are reported. For a few representative examples, spectroelectrochemical measurements were used to clarify the electron exchange process. In addition, a detailed electron paramagnetic resonance (EPR) study was performed to estimate the extent of delocalization of the generated radical cations. In particular, electron nuclear double resonance spectroscopy (ENDOR) was used to determine the coupling constants. DFT calculations were conducted to corroborate the EPR spectroscopic data

Inexpensive and Efficient Ullmann Methodology To Prepare Donor-Substituted Porphyrins

The preparation of porphyrins functionalized with one or two carbazoles (or phenoxazines) is described. The electron donors were introduced into one or two porphyrin <i>meso</i> positions by using the inexpensive Ullmann coupling procedure. Very good yields were obtained, and for two new compounds, the X-ray structures were solved. Preliminary electrochemical data coupled with electronic spectroscopy are also reported