Κυκλομεταλλικά σύμπλοκα του Pt (II) με 2-φαινυλπυριδίνη και 2,2΄-διπυριδίνη (Master thesis)

Γεωργιανού, Μαριαλένα


This study describes the synthesis of Pt(II) cyclometallated complexes with general formula [Pt(ppy)(bpy)]X, where ppy = 2-phenylpyridine, bpy = 2,2’-bipyridine and X = F-, Cl-, Br-, I-. There were also used other anions, such as PF6-, ClO4- and NO3-, in order to investigate the possible role of the counterions in the complexes. These complexes were studied with various analytical methods, like mass spectrometry, thermal analysis and conductivity, as well as with many spectroscopical methods, such as UV- Vis spectroscopy, powder X- Ray diffraction and nuclear magnetic resonance. The used NMR techniques were 1H NMR, 195Pt NMR, COSY, TOCSY and NOESY. The diffusion coefficient was calculated via DOSY NMR experiments, whilst 1H NMR experiments helped the investigation of concentration and temperature in some of the complexes. In addition, the reactivity of the prepared complexes with dmso was also studied and it was found that only the ones with a halogen as a counterion, and in particular Cl-, Br-, I-were decomposed, while the complexes with the other counterions as PF6-, ClO4- and NO3-- were stable. The resulting complexes have the general structure [PtX(ppy(dmso)], in which X is one of the tree halogens. These complexes were studied only with 1H and 195Pt NMR spectroscopy and their diffusion coefficient was also calculated via DOSY NMR experiments. From the above studies we conclude that in the first type of complexes, [Pt(ppy)(bpy)]X, the halogens are part of the complex structure and they influence the solubility of the complexes in aqueous media which is due to the ionic character of its interaction with the platinum center. The [Pt(ppy)(bpy)]F and [Pt(ppy)(bpy)]Cl complexes were found to aggregate in aqueous solution but their aggregations consist of a different number of units, indicating that the aggregation degree depends on the nature of halogen too. The [Pt(ppy)(bpy)]I adopts a square pyramidal geometry and shows fluxional behavior. In the second type of complexes, [PtX(ppy)(dmso)], one can assume that a hydrogen bond is formed between the halogen and the H6’ proton of the 2-phenylpyridine ligand. The strength of this bond is related with the δ- of the halogen that is also related with the nature of the platinum – halogen bond.
Institution and School/Department of submitter: Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας
Subject classification: Σύμπλοκες ενώσεις
Keywords: Σύμπλοκα Pt(ΙΙ),2-φαινυλπυριδίνη,2,2΄-διπυριδίνη,Inorganic chemistry,Pt (II) compouds,2-phenylpyridine,2,2 - bipyridine
URI: http://olympias.lib.uoi.gr/jspui/handle/123456789/29412
Appears in Collections:Διατριβές Μεταπτυχιακής Έρευνας (Masters)

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