Transformations of Energy-Related Small Molecules at Dinuclear Complexes

by Jana Lücken
Doctoral thesis
Date of Examination:2020-11-04
Date of issue:2021-02-05
Advisor:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Inke Siewert
Referee:Prof. Dr. Sven Schneider
Referee:Prof. Dr. Ricardo Mata
Referee:Dr. Nathalie Jun.-prof. Kunkel
Referee:Dr. Michael John
Persistent Address: http://dx.doi.org/10.53846/goediss-8392

 

 

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Abstract

English

The urgent need for the development of carbon-neutral energy conversion schemes has inspired chemists worldwide to investigate catalytic water splitting using sunlight as the energy source. A key component for the preparation of devices employing this process is the water oxidation catalyst (WOC), and understanding the factors that govern its catalytic performance is among the major challenges. Herein, two highly water-soluble dinuclear ruthenium complexes were synthesized and proven capable of chemical, electrochemical and photochemical water oxidation, revealing the surprising stability of a bridging DMSO ligand. Dinuclear copper and cobalt complexes were also investigated as WOCs, showing degradation under the catalytic conditions. Magnetic susceptibility measurements on related cobalt complexes further displayed interesting magnetic behavior with a slow relaxation of the magnetization. Moreover, a glance was cast at dioxygen activation. In this regard, the acetate-bridged dicopper(II) complex was first reduced, affording the dicopper(I) compound via a unique mixed-valent Cu(I)Cu(II) intermediate. Subsequent oxygen activation yielded both superoxo and peroxo species. Surprisingly, the reduction of the formate-bridged dicopper(II) compound generated a hexanuclear copper(I) hydride complex after decarboxylation.
Keywords: water oxidation; oxygen activation; formic acid decarboxylation; ruthenium; cobalt; copper; dinuclear complexes; copper hydride; transition metal complexes; coordination chemistry; small molecule activation; catalysis; WOC; small molecule transformation; SMM; magnetism
 
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