Synthesis of carbon rich organometallic complexes for investigation of electronic communication bewteen metal centres

Campbell Mackenzie

Research output: ThesisDoctoral Thesis

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[Truncated] This thesis presents work that has been performed in the synthesis of a range of mono and bimetallic organometallic complexes. The electronic and structural characteristics of these complexes have been investigated. Of particular interest is the intramolecular communication between metal centres that can be observed for the bimetallic complexes. Understanding electronic communication is a fundamental concern for the growing field of molecular electronics. The introduction presents a brief background to the field of molecular electronics. This is followed by an overview of mixed valence complexes and the application to the study of electronic communication. The introduction concludes by presenting the ligands that were studied in this thesis, along with a summary of spectroelectrochemistry and theoretical studies as they were applied to the complexes synthesised here.
The majority of the complexes studied in this thesis contained a ruthenium σ-alkynyl moiety. Chapter 2 begins with a summary of the properties and synthesis of transition metal σ-alkynyl complexes. The synthesis and characterisation of ruthenium σ-alkynyl complexes of the widely studied ligand 5-ethynyl-2,2’-bipyridine is presented along with a spectroelectrochemical and theoretical investigation of the complexes.
Chapter 3 introduces the coordination chemistry of the 2,2’-bipyridine moiety. The complexes synthesised in Chapter 2 were used as metalloligands for the coordination of an additional metal centre to the bipyridyl moiety. The bimetallic complexes were characterised and studied by spectroelectrochemical and theoretical methods. The homobimetallic complexes that were synthesised showed Class II mixed valence behaviour resulting from weak electronic communication.
Chapter 4 uses the less studied ligand 4-ethynyl-2,2’-bipyridine to synthesise and characterise a range of mono and bimetallic complexes that were analogous to those synthesised in Chapters 2 and 3. Evaluation of the electronic communication through this ligand by spectroelectrochemical and theoretical methods showed Class II mixed valence behaviour. Comparison of the electronic communication exhibited by complexes in Chapters 3 and 4 showed that there was better electronic communication through the 4-ethynyl-2,2-bipyridine isomer of the ligand.
Original languageEnglish
QualificationDoctor of Philosophy
  • Koutsantonis, George, Supervisor
  • Baker, Murray, Supervisor
Publication statusUnpublished - 2015


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