Tuning of the Excited State Properties of Ruthenium(II)-Polypyridyl Complexes

• Main Author: Abrahamsson, Maria
• Format: Doctoral Thesis
• Language: English
• Published: Uppsala universitet, Acceleratormasspektrometrigruppen 2006
• Subjects: Physical chemistry; Artificial photosynthesis; Ruthenium(II); Bistridentate complexes; Excited state lifetime; Linear donor-photosenstizer-acceptor arrays; Temperature dependence; Excited state decay; Fysikalisk kemi
• Online Access: http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-7230; http://nbn-resolving.de/urn:isbn:91-554-6707-5

Processes where a molecule absorbs visible light and then converts the solar energy into chemical energy are important in many biological systems, such as photosynthesis and also in many technical applications e.g. photovoltaics. This thesis describes a part of a multidisciplinary project, aiming at a functional mimic of the natural photosynthesis, with the overall goal of production of a renewable fuel from sun and water. More specific, the thesis is focused on design and photophysical characterization of new photosensitizers, i.e. light absorbers that should be capable of transferring electrons to an acceptor and be suitable building blocks for supramolecular rod-like donor-photosensitizer-acceptor arrays. The excited state lifetime, the excited state energy and the geometry are important properties for a photosensitizer. The work presented here describes a new strategy to obtain longer excited state lifetimes of the geometrically favorable Ru(II)-bistridentate type complexes, without a concomitant substantial decrease in excited state energy. The basic idea is that a more octahedral coordination around the Ru will lead to longer excited state lifetimes. In the first generation of new photosensitizers a 50-fold increase of the excited state lifetime was observed, going from 0.25 ns for the model complex to 15 ns for the best photosensitizer. The second generation goes another step forward, to an excited state lifetime of 810 ns. Furthermore, the third generation of new photosensitizers show excited state lifetimes in the 0.45 - 5.5 microsecond region at room temperature, a significant improvement. In addition, the third generation of photosensitizers are suitable for further symmetric attachment of electron donor and acceptor motifs, and it is shown that the favorable properties are maintained upon the attachment of anchoring groups. The reactivity of the excited state towards light-induced reactions is proved and the photostability is sufficient so the new design strategy has proven successful.