The thesis aims at developing techniques in solid state nuclear magnetic resonance (ssNMR) of paramagnetic metal-organic and inorganic systems in combination with electron paramagnetic resonance (EPR) spectroscopy and quantum chemical methods such as density functional theory (DFT).Solid state NMR signals of paramagnetic systems suffer from severe loss of sensitivity and resolution due to large hyperfine interactions. Among all the interactions seen in ssNMR, the interaction between the unpaired electron(s) and the observed nucleus leading to hyperfine interaction in paramagnetic solids is large in magnitude. Large broadening due to fast relaxation in paramagnetic systems on the one hand limits the excitation of the nuclei using conventional probes thereby causing severe loss in sensitivity and resolution of ssNMR signals. On the other hand the large shifts due to Fermi-contact interaction mask the diamagnetic chemical shifts (which are rich source of chemical group information) and make signal assignment difficult. The conventional techniques developed for solid state NMR of diamagnetic systems are inefficient for paramagnetic systems. These factors have led ssNMR of paramagnetic systems to be an unexplored topic for decades.Recently Ishii and co-workers have circumvented some of these problems using very-fast magic angle spinning (VFMAS).1 Spinning the sample at MAS frequencies >30 kHz drastically enhances the sensitivity and resolution of ssNMR signals in paramagnetic complexes. We have used the VFMAS approach and have shown how to cope with moderate hyperfine interactions in ssNMR of organic (cyclam and acetylacetonate) and inorganic (alkaline-copper pyrophosphates) systems with transition metal ions such as CuII, NiII and VIV as paramagnetic center. On the one hand Fermi-contact interaction which is responsible for large shifts up to 100 ppm in 1H and 1000 ppm in 13C and 31P cause severe problems for signal assignment. But on the other hand it also leads to better spectral dispersion and hence improve the resolution of the ssNMR signals. We were able to exploit this idea and a well resolved 13C and even 1H solid state NMR spectrum in paramagnetic metal-organic systems was obtained using a simple Hahn-echo experiment. This is usually not possible, since 1H NMR in diamagnetic solids suffer from large broadening of 100 kHz due to 1H-1H homonuclear dipolar coupling. Furthermore fast relaxation in paramagnetic systems allows one to reduce the interscan delay and thereby repeat the experiments several times in a given time and improve the signal to noise ratio. This compensates for loss in sensitivity more often due to fast relaxation in paramagnetic systems.Fermi-contact shifts are characteristics of unpaired electron spin density in a molecule. Using quantum chemical methods such as DFT one can calculate the theoretical Fermi-contact shifts.2 We have compared the experimental 13C ssNMR shifts with shifts from DFT calculation in paramagnetic metal –cyclam and –acetylacetonate complexes and have assigned the 13C signals. For assignment of 1H, a 2D version of dipolar INEPT (insensitive nuclei enhancement by polarization transfer) was used. In some cases such as the Cu-cyclam complex, a very well resolved 1H ssNMR spectrum motivated us to try 1H-1H homonuclear correlation experiment. We obtained several important cross peaks with a relatively simple pulse sequence. We used the dipolar connectivity information from it to complete the 1H assignment.One of the important aims of the thesis was to find a way to measure the metal-carbon distances using solid state NMR relaxation rates. In paramagnetic metal-organic complexes the carbon-13 relaxation caused by the dipolar interaction with the unpaired electron depends on the distance of the carbon atoms to the central metal ion, therefore its rates in principle contain structural information... / The thesis aims at developing techniques in solid state nuclear magnetic resonance (ssNMR) of paramagnetic metal-organic and inorganic systems in combination with electron paramagnetic resonance (EPR) spectroscopy and quantum chemical methods such as density functional theory (DFT).Solid state NMR signals of paramagnetic systems suffer from severe loss of sensitivity and resolution due to large hyperfine interactions. Among all the interactions seen in ssNMR, the interaction between the unpaired electron(s) and the observed nucleus leading to hyperfine interaction in paramagnetic solids is large in magnitude. Large broadening due to fast relaxation in paramagnetic systems on the one hand limits the excitation of the nuclei using conventional probes thereby causing severe loss in sensitivity and resolution of ssNMR signals. On the other hand the large shifts due to Fermi-contact interaction mask the diamagnetic chemical shifts (which are rich source of chemical group information) and make signal assignment difficult. The conventional techniques developed for solid state NMR of diamagnetic systems are inefficient for paramagnetic systems. These factors have led ssNMR of paramagnetic systems to be an unexplored topic for decades.Recently Ishii and co-workers have circumvented some of these problems using very-fast magic angle spinning (VFMAS).1 Spinning the sample at MAS frequencies >30 kHz drastically enhances the sensitivity and resolution of ssNMR signals in paramagnetic complexes. We have used the VFMAS approach and have shown how to cope with moderate hyperfine interactions in ssNMR of organic (cyclam and acetylacetonate) and inorganic (alkaline-copper pyrophosphates) systems with transition metal ions such as CuII, NiII and VIV as paramagnetic center. On the one hand Fermi-contact interaction which is responsible for large shifts up to 100 ppm in 1H and 1000 ppm in 13C and 31P cause severe problems for signal assignment. But on the other hand it also leads to better spectral dispersion and hence improve the resolution of the ssNMR signals. We were able to exploit this idea and a well resolved 13C and even 1H solid state NMR spectrum in paramagnetic metal-organic systems was obtained using a simple Hahn-echo experiment. This is usually not possible, since 1H NMR in diamagnetic solids suffer from large broadening of 100 kHz due to 1H-1H homonuclear dipolar coupling. Furthermore fast relaxation in paramagnetic systems allows one to reduce the interscan delay and thereby repeat the experiments several times in a given time and improve the signal to noise ratio. This compensates for loss in sensitivity more often due to fast relaxation in paramagnetic systems.Fermi-contact shifts are characteristics of unpaired electron spin density in a molecule. Using quantum chemical methods such as DFT one can calculate the theoretical Fermi-contact shifts.2 We have compared the experimental 13C ssNMR shifts with shifts from DFT calculation in paramagnetic metal –cyclam and –acetylacetonate complexes and have assigned the 13C signals. For assignment of 1H, a 2D version of dipolar INEPT (insensitive nuclei enhancement by polarization transfer) was used. In some cases such as the Cu-cyclam complex, a very well resolved 1H ssNMR spectrum motivated us to try 1H-1H homonuclear correlation experiment. We obtained several important cross peaks with a relatively simple pulse sequence. We used the dipolar connectivity information from it to complete the 1H assignment.One of the important aims of the thesis was to find a way to measure the metal-carbon distances using solid state NMR relaxation rates. In paramagnetic metal-organic complexes the carbon-13 relaxation caused by the dipolar interaction with the unpaired electron depends on the distance of the carbon atoms to the central metal ion, therefore its rates in principle contain structural information...

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Akademisk avhandling--oorganisk Kemi--Göteborgs universitet, 2002. / Bibliogr. p. 86-92.

Thèse de doctorat : Génie des procédés : Vandoeuvre-les-Nancy, INPL : 2005. / Titre provenant de l'écran-titre. Bibliogr.

Thèse de doctorat : Chimie et Physico-chimie Moléculaire : Nancy 1 : 2007. / Titre provenant de l'écran-titre. Bibliogr.

Thèse de doctorat : Episthémologie, histoire des sciences et des techniques : Paris 10 : 2007. / Titre provenant de l'écran-titre.

Reproduction de : Thèse de doctorat : Mécanique : Metz : 2008. / Titre provenant de l'écran-titre. Notes bibliographiques. Index.

Thèse de doctorat : mécanique et matériaux : Ecole centrale de Paris : 2009. / Titre provenant de l'écran-titre. Bibliogr. 161 réf.

Reproduction de : Thèse de doctorat : Physique : Lyon 1 : 2006. / Titre provenant de l'écran titre. Bibliogr. p.201-207.

Thèses (M.Sc.)--Université de Sherbrooke (Canada), 1997. / Titre de l'écran-titre (visionné le 20 juin 2006). Publié aussi en version papier.