Dinuclear Manganese Complexes for Artificial Photosynthesis : Synthesis and Properties

• Main Author: Anderlund, Magnus
• Format: Doctoral Thesis
• Language: English
• Published: Stockholms universitet, Institutionen för organisk kemi 2005
• Subjects: Crystal Structure; Artificial photosynthesis; Manganese complex; Organic chemistry; Organisk kemi
• Online Access: http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-396; http://nbn-resolving.de/urn:isbn:91-7155-018-6

This thesis deals with the synthesis and characterisation of a series of dinuclear manganese complexes. Their ability to donate electrons to photo-generated ruthenium(III) has been investigated in flash photolysis experiments followed by EPR-spectroscopy. These experiment shows several consecutive one-electron transfer steps from the manganese moiety to ruthenium(III), that mimics the electron transfer from the oxygen evolving centre in photosystem II. The redox properties of these complexes have been investigated with electro chemical methods and the structure of the complexes has been investigated with different X-ray techniques. Structural aspects and the effect of water on the redox properties have been shown. One of the manganese complexes has been covalently linked in a triad donor-photosensitizer-acceptor (D–P–A) system. The kinetics of this triad has been investigated in detail after photo excitation with both optical and EPR spectroscopy. The formed charge separated state (D––P–A+) showed an unusual long lifetime for triad based on ruthenium photosensitizers. The thesis also includes a study of manganese-salen epoxidation reactions that we believe can give an insight in the oxygen transfer mechanism in the water oxidising complex in photosystem II.