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Acetylenic phenanthroline analogues, phenanthrolino-fused benzodehydroannulenes and their Ru(II)-complexes.

Ott, Sascha M.; (2002) Acetylenic phenanthroline analogues, phenanthrolino-fused benzodehydroannulenes and their Ru(II)-complexes. Doctoral thesis (Ph.D.), University College London. Green open access

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Abstract

The unique photophysical properties together with the photo- and electrochemically readily accessible Ru(II)/Ru(III) redox couple have led to many applications of polypyridine ruthenium(II)-complexes over the last three decades. For example, they have emerged as key players in the design of light harvesting devices, as photonic nanowires and as luminescent probes for the study of biomolecules such as DNA and lipid vesicles. Over the last decade, the field of dehydroannulene chemistry has experienced a renaissance as a result of the interesting material properties as well as the feasibility with which electronic communication is established through the all-carbon framework. In this thesis an attempt has been made to combine the two fields of Ru(II)polypyridine and dehydroannulene chemistry by synthesising a rigid, planar phenanthrolino-fused benzodehydroannulene which is co-ordinated to (bpy)2Ru fragments. The work presented herein describes the synthesis of a number of differentially terminated acetylenic pyrazino[2,3-f][l,10] phenanthroline (pyzphen) heterocycles and their corresponding [(bpy)2Ru(pyzphen)]2+ and [(phen)2Ru(pyzphen)]2+ (bpy = 2,2'- bipyridine, phen = [l,10]phenanthroline) complexes as precursors for the construction of Ru co-ordinated dehydroannulenes. It is shown that the photophysical and the electrochemical properties of both the free ligands and their Ru(II) complexes are clearly modified by the presence of the alkynyl substituents. In later parts of this thesis, several attempts to prepare a Ru co-ordinated phenanthrolino-fused benzodehydroannulene are described, culminating in the synthesis of a (bpy)2Ru co-ordinated, dppz-fiised (dppz = dipyrido[3,2-a:2',3'-c]phenazine) dehydro[12]annulene. The electronic coupling between the two dppz chelates through the dehydroannulene scaffold could be established by spectroscopic and electrochemical techniques, whereas the Ru centres seem to be largely invariant to the presence of a second metal centre in close proximity.

Type: Thesis (Doctoral)
Qualification: Ph.D.
Title: Acetylenic phenanthroline analogues, phenanthrolino-fused benzodehydroannulenes and their Ru(II)-complexes.
Open access status: An open access version is available from UCL Discovery
Language: English
Additional information: Thesis digitised by ProQuest.
URI: https://discovery.ucl.ac.uk/id/eprint/10104482
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