Sensitizing mechanisms, reaction mechanisms and reactive intermediate states in photocatalytic reactions on time scales from femto- to microseconds
b'The development of renewable energy sources depicts a constantly growing interdisciplinary research field. Beyond photovoltaics chemical photocatalysis plays a small role, but is gaining more and more importance. In photocatalysis, light serves as an energy source for the chemical conversion of certain molecules. However, not only the application of photocatalysis as energy source but also the utilization of photocatalysis in chemical synthesis has attracted a deep scien- tific interest. For the optimization of photocatalytic systems a fundamental understanding oft the underlying processes is more than essential. Thereby, transient absorption spectroscopy has proved to be a very useful tool. On the one hand, the operation of a setup for transient absorption spectroscopy and on the other hand the systematic data evaluation requires physical and mathe- matical skills whereas the results cannot be interpreted without deep chemical knowledge. With- in the framework of the present thesis the cooperation between the fields of organic chemistry and physics has turned out as a very productive cooperation. Sensitizing mechanisms, reaction mechanisms and reactive intermediate states in photocatalytic reactions on time scales from femto- to microseconds are the object of the present work.\\nThe present thesis will prove that the analysis of measurement data on the basis of established standard methods, such as the fitting of a sum of exponential functions to the temporal evolution of the measured signal, often is not sufficient for a complete interpretation of the data. Only a data analysis precisely adapted to the problem can lead to a fundamental understanding of the underlying processes.\\nIn the first part of the present thesis, the focus lies on light-induced intramolecular charge transfer processes. Marcus Theory, which depicts the theoretical background, will be briefly in- troduced. On the basis of a molecular donor-bridge-acceptor system it will be shown that the damping coefficient \\u03b2 is not sufficient to differ unambiguously between coherent tunneling and incoherent hopping mechanism.\\nFlavin-capped DNA hairpins serve as a model for the investigation of intramolecular charge transfer processes. After photo-excitation, flavin induces a hole which migrates through the DNA strand. It will be shown that an adapted base sequence allows for quantum yields of \\u03a6CS = 14% for long-lived charge separated states.\\nIn the next section it will be discussed if the building blocks of the DNA are adapted to serve as chiral backbone for enantioselective photocatalysis. The conformation-dependent charge- transfer dynamics in benzophenone-DNA dinucleotides will be put on solid ground with the help of Marcus Theory. It will be shown that these dinucleotides are generally not suited to serve as an inert backbone for every kind of photochemical reaction.\\nIn the following section a true bimolecular photocatalytic reaction will be discussed. Flavin serves as photocatalyst for the conversion of an alcohol to the corresponding aldehyde. A pre- cisely adapted data analysis allows and exact quantification of the diffusion controlled reaction dynamics on the ps time scale. The understanding of the process allows optimizing the reaction conditions. The targeted utilization of triplet chemistry within this reaction can help to increase the quantum yield for product formation.\\nAs photo-induced charge transfer processes have been intensively discussed, the focus in the second part of the thesis lies on the [2+2] photocycloaddition. As basis for the interpretation of subsequent measurements, the [2+2] photocycloaddition of substituted quinolones will be inves- tigated. The formation of the cyclobutane ring in which the quinolone triplet state plays the cen- tral role will be characterized and quantified on the time scale from ps to ns. Afterwards the [2+2] photocycloaddition of substituted quinolones will be initiated by a chiral xanthone-based photocatalyst. It will be shown that within this catalyst-substrate complex in which both constit- uents have a distance of only few \\xc5ngstr\\xf6ms, new electronic properties appear. The photo- excitation of a new electronic state not only initiates the [2+2] photocycloaddition of the quino- lone but also depicts a new sensitizing mechanism, which has to the author\\u2019s best knowledge not been observed in photocatalysis of organic molecules. The quinolone triplet state does not appear in this mechanism. The question, if this mechanism can be transferred to other photocatalytic systems has to be answered within the framework of further studies.'