Controlling Charge and Energy Transfer Processes in Artificial Photosynthesis : From Picosecond to Millisecond Dynamics
Sammanfattning: This thesis describes an interdisciplinary project, where the aim is to mimic the initial reactions in photosynthesis. In photosynthesis, the absorption of light is followed by the formation of charge-separated states. The energy stored in these charge-separated states is further used for the oxidation of water and reduction of carbon dioxide. In this thesis the photo-induced processes in a range of supramolecular complexes have been investigated with time resolved spectroscopic techniques. The complexes studied consist of three types of units; photosensitizers (P) capable of absorbing light, electron acceptors (A) that are easily reduced and electron donors (D) that are easily oxidised. Our results are important for the future design of artificial photosystems, where the goal is to produce hydrogen from light and water. Two molecular triads with a D-P-A architecture are presented. In the first one, a photo-induced charge-separated state was formed in an unusually high yield (φ>90%). In the second triad, photo-irradiation led to the formation of an extremely long-lived charge-separated state (τ = 500 ms at 140K). This is also the first synthetically made triad containing a dinuclear manganese unit as electron donor.Further, two sets of P-A dyads are presented. In both, the expected photo-induced reduction of the electron acceptor is diminished due to competing energy transfer to the triplet state of the acceptor.Finally, a P-P-A complex containing two separate photosensitizers is described. The idea is to produce high-energy charge-separated states by using the energy from two photons.
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