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Identifier uch.chemistry.phd//1998dafnomili
Title Σύνθεση και χαρακτηρισμός διμερών διμεταλλικών πορφυρινικών σύμπλοκων με δεσμούς Rh-Tl και Rh-In
Author Δαφνομήλη, Δήμητρα Ι
Thesis advisor Κουτσολέλος, Αθανάσιος
Abstract In the present thesis the synthesis and the physicochemical characterization of a series of Dimeric Dimetallic metalloporphyrines are presented. It is focused in a non well studied chemical bond, the single bond between a transition and a non-transition metal. New monomeric complexes of Tl and In, dimeric complexes with a new chemical bond between Rh and Tl and complexes with Rh-In bond with different macrocycles have been synthesized. Their properties have been studied by U.V.-Vis, I.R., N.M.R., 205 Tl N.M.R. EXAFS X-Ray. For the dimeric complexes their photochemical reactivity as well as their reactivity towards different substrates have been studied. All the complexes have optical properties of “hyper” type with blue-shifted Soret band. This is characteristic of complexes with strong π-π interactions. These interactions can be modified mainly by the non-transition metal and the metalloporphyrin of the non transition metal. N.M.R studies, and the comparison of the chemical shifts of the protons of the two different macrocycles reveal that the differences of the chemical shifts are related to the distance of the two rings and the distance of the bimetallic bond. 205Tl N.M.R chemical shifts range between 2000-3000 ppm for the monomeric metalloporphyrins. For the dimeric complexes with Tl-Rh bond the spectra are more than 2000 ppm shifted related to the monomeric complexes while for the first time the magnitude of spin-spin coupling constants between 205Tl and 103Rh have been measured. These large differences in chemical shifts are related to the change in electronic environment of the Tl nucleous because of the formation of the bond. Finally the first EXAFS experiment show a distance of Rh-Tl bond longer than Rh-In bond.
Language Greek
Issue date 1998-12-01
Collection   School/Department--School of Sciences and Engineering--Department of Chemistry--Doctoral theses
  Type of Work--Doctoral theses
Permanent Link https://elocus.lib.uoc.gr//dlib/6/6/a/metadata-dlib-1998dafnomili.tkl Bookmark and Share
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