investigated the ultrafast excited-state dynamics of a series of donor-acceptor systems from simple dyads to synthetic supramolecular architectures in rigid structures. By doing this, I was lucky to be involved in many interesting projects, which allowed me to explore different aspects and factors that can affect the efficiency and rate of electron and energy transfer processes.
The research on simple donor-acceptor pairs gave us an understanding of how simple chemical manipulations, solvent polarity and excitation wavelength variation can significantly affect the photophysics of the investigated systems and lead to different processes on different timescales, and sometimes even in opposite directions. Additionally, the reaction rate dependence of electron transfer between a donor and an acceptor was also tested on the increasing number of electron acceptors covalently attached to a single donor.
Another important aspect that can affect electron transfer process occurs when donor and acceptor are separated by a molecular spacer or bridge. In such a case, the electron transfer process can depend not only on the nature of donor and acceptor moieties but also be mediated by the length and nature of the bridge. Moreover, two possible mechanisms of electron transfer can be operative in such systems: (i) hopping mechanism, when the bridge is directly involved in the process, resulting in the temporal localization of the electron on the bridge, or (ii) superexchange mechanism, when the electronic coupling is controlled by mixing the initial and final states of the system with high energy states of the bridge. Therefore, we investigated two sets of donor-bridge-acceptor systems with emphasis on the role of the bridge on electron transfer.
Finally, we studied the photophysics of a system that can find potential applications in optoelectronic and photovoltaic. For this, we worked on a system of high sophistication that can mimic the process of light harvesting and conversion. In nature, photosystems are composed of a large number of identical self-organized chromophores; this is advantageous for increasing the absorption cross-section. However, organization of many synthetic multichromophoric systems in supramolecular architectures can lead to the interaction between the nearby chromophores and thus considerably change the photophysical properties. That is why we compared the excited-state dynamics of a model multichromophoric system in solution with that of a supramolecular surface architecture.
Whereas, in the all previously discussed cases we have been interested in the single-electron transfer reactions, we also worked on light-driven accumulation of multiple electrons or holes on a certain molecular unit. Charge accumulation is necessary for artificial photosynthesis, because fuel-forming reactions such as H2 production or CO2 reduction require multiple redox equivalents. Therefore, a molecular pentad comprising a central multielectron donor and two flanking photosensitizer-acceptor moieties was examined on its ability of accumulating one and two positive charges at the central donor.
The investigation of very rich excited-state dynamics and complex photophysics of the systems explored in this thesis was possible due to a combination of steady-state and time-resolved spectroscopy. Femto- and picosecond resolved techniques allowed us to measure photophysical processes in a real time, and to cover the time window of interest from 100 femtosecond to millisecond. Time-resolved fluorescence techniques were extremely useful to explore precisely the fluorescence dynamics, while transient absorption allowed to get a full picture by monitoring also non-emissive and dark states. The broadband detection permitted us to identify the intermediate reaction products that might be missed in single-wavelength detection measurements.
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