In this work , metal functional polymers, namely Cr-PS-b-P2VP, Co-PS-b-P2VP, Au-PS-b-P2VP, Fe-PS-b-P2VP and Mo-PS-b-P2VP were prepared by thermal reaction of hexacarbonylchromium, Cr(CO)6, octacarbonyldicobalt,Co2(CO)8, hydrogentetrachloroaurate(III), H(AuCl4).4H2O, trichloroiron(III), FeCl3.6H2O, molybdenum(VI)oxide, MoO3 and PS-b-P2VP. TEM images indicated formation of AuIII, Cr and Co nanoparticles. On the other hand, crystalline structures were detected for Fe-PS-b-P2VP and Mo-PS-b-P2VP. Samples involving nanoparticles were further characterized by FTIR, UV-Vis and direct pyrolysis mass spectroscopy techniques. FTIR analysis indicated dissapearance of characteristic carbonyl peaks of Cr(CO)6 and Co2(CO)8 for Cr-PS-b-P2VP and Co-PS-b-P2VP samples. The appearance of a peak at about 467 cm-1 supported the formation of metal-nitrogen bond. Pyrolysis mass spectrometry analysis showed an increase in the thermal stability of P2VP chains involving coordinated pyridine units. The thermal stability of these chains increased in the order Co&lt / Cr &lt / Au3+ indicating stronger coordination in the same order.

Recently, the use of block copolymers in preparation of nanocomposites has received great attention as they form well-defined micelles. In this work, the synthesis of different metal functional copolymers, nano structural metal composites and investigation of their reaction mechanism and thermal characteristics by pyrolysis mass spectroscopy have been aimed. Namely, polyisoprene-block-poly2vinylpyridine, (PI-b-P2VP) and poly2vinylpyridine-block-polymetylmethacrylate, (PMMA-b-P2VP) were used as block copolymers and the thermal reaction of these copolymers with two different transition metal complexes Cr(CO)6 and HAuCl4.3H2O were investigated which mostly lead to the coordination of metal through nitrogen atom of the pyridine ring which then degrates to form nano particles. The samples were further characterized by TEM, ATR-FT-IR, UV-Vis and Direct-Pyrolysis Mass Spectroscopy techniques. TEM images proved the formation of nanoparticles and the results showed that synthesized Au nanoparticles have 2 to 3 fold larger size than Cr nanoparticles. ATR-FT-IR spectrum of metal functional copolymers showed that the disappearance of characteristic peaks of pyridine stretching and bending mode when metal coordinates to the pyridine nitrogen. Furthermore, the spectrum indicated the appearance of a new absorption peak at around 740 cm-1 which may be a clue for the coordination of gold(III) ion to the pyridine nitrogen. Different from chromium case, in the spectrum of Au3+-(PMMA-b-P2VP), CO stretching frequency of PMMA which may appear at around 1720&ndash / 1718 cm-1 decreased in intensity while a new absorption peak appeared at around 1600 cm-1. This results reveals that electron deficient gold (III) ion prefers the coordination from both donor atoms namely carbonyl oxygen PMMA and pyridine nitrogen of P2VP in order to compensate its electron deficiency. In the UV-Vis spectrum of copolymers, Cr-functional copolymers showed a sharp absorption peak appeared at around 290 nm is attributed to a MLCT transition from chromium atom to * orbital of pyridine group. Furthermore, Au-functional copolymers showed a completely new absorption band at around 320 nm which can be associated again with a LMCT transition since gold is electron deficient and more willing to accept electrons from the ligand. Pyrolysis mass spectrometry analysis showed that poly2vinylpyridine blocks for each copolymers were affected similarly but polyisoprene block was not affected much from the coordination of metal compared to poly(methyl methacrylate) block in copolymers. For (PI-b-P2VP), Au3+ coordination to copolymer resulted in the higher thermal stability compared to Cr coordination. For (PMMA-b-P2VP), different from Cr, Au3+ coordination to P2VP nitrogen atom was extensive and PMMA based products changed drastically due to the coordination of electron deficient Au3+ to PMMA carbonyl group.

Ce travail de thèse est consacré à la synthèse de porphyrines fusionnées à des cycles imidazolium et à l’utilisation de ces derniers comme précurseurs de ligands carbènes N-hétérocycliques (NHC). Ces composés possèdent donc deux sites de coordination, interne (le macrocycle) et externe (le ligand NHC), permettant la synthèse de complexes dinucléaires. Cette étude est principalement axée sur la synthèse de métalloporphyrines conjuguées avec des complexes d’or(I) périphériques de type [(NHC)AuCl]. En vue d’application en thérapie photodynamique (PDT), la fonctionnalisation de ces complexes par des carbohydrates (mannose) a été réalisée par substitution des ligands chlorures des complexes d’or(I) périphériques. Les tests biologiques sur cultures cellulaires montrent une nette potentialisation des propriétés photodynamiques des photosensibilisateurs comportant des ligands mannoses liés à l’or(I). Suite à cette étude, la synthèse de porphyrines fusionnées à deux cycles imidazolium a été réalisée permettant pour la première fois la synthèse de complexes trinucléaires de type Au/M/Au (M = métal interne dans la porphyrine) possédant différentes géométries. Ces composés ont ouvert des perspectives intéressantes dans le but d’obtenir des photosensibilisateurs possédant deux groupements carbohydrates à leur périphérie. De plus, il a été mis en évidence que les complexes trinucléaires de type Au/Zn/Au peuvent être utilisés comme briques de construction moléculaires pour la synthèse de polymères organométalliques en vue d’applications en (photo)catalyse. / This PhD work is devoted to the synthesis of porphyrins fused to imidazolium rings and their use as precursors of N-heterocyclic carbene ligands (NHC). Therefore, these compounds possess two coordination sites, the internal (the macrocycle) and the external (the NHC ligand) ones, allowing the synthesis of dinuclear complexes. This study is mainly centered on the synthesis of metalloporphyrins conjugated with peripheral gold(I) complexes such as [(NHC)AuCl]. In view of applications in photodynamic therapy (PDT), the functionalization of these complexes by carbohydrates was achieved through the substitution of chloride ligands of peripheral gold(I) complexes. Biological tests on cell cultures show a clear potentialization of the photodynamic properties of the photosensitizers bearing mannose ligands bound to gold(I). Following this study, the synthesis of porphyrins fused to two imidazolium rings was achieved allowing for the first time the synthesis of trinuclear species such as Au/M/Au (M = inner metal in the porphyrin core) with different geometries. These compounds open interesting perspectives in view of obtaining photosensitizers having two carbohydrates at their periphery. Moreover, it was shown that trinuclear species such as Au/Zn/Au can be used as molecular building-blocks for the synthesis of organometallic polymers in view of applications in (photo)catalysis.