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Ultrafast Excited-State Processes of Re Carbonyl-Diimine Complexes: from Excitation to Photochemistry

Date Do, 30.06.2011 - Do, 30.06.2011
Time 10.15
Speaker Prof. Antonín Vlcek, Jr., School of Biological and Chemical Sciences, Queen Mary, University of London, Mile End Road, London E1 4NS, United Kingdom., J. Heyrovský Inst. of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, CZ-18
Location Universität Bern, Institut für Angewandte Physik, Gebäude exakte Wissenschaften, Hörsaal B77, Sidlerstrasse 5, 3012 Bern
Program Rhenium (I) complexes of the type fac-[Re(L)(CO)3(N,N)]n show exceptionally rich excited-state behavior and redox chemistry. They are thermally and photo chemically robust and highly flexible synthetically. Broad structural variations of the N,N ligand as well as the axial ligand L are possible, allowing us to incorporate these chromophores into a range of media, attach them to proteins, intercalate into DNA or make them parts of supramolecules designed to perform specific functions. The same structural and medium variations affect the nature and energetic order of low-lying excited states and, thus, the spectroscopy, photophysics, photochemistry and electrochemistry of the Re chromophore. In this seminar, we will focus on dynamic aspects of the processes triggered by electronic excitation and follow the evolution of excited Re chromophores from the instant of the photon absorption until the ground state is recovered or a photochemical product formed. We will proceed from the intersystem crossing, which ensues the photon absorption, to the hot 3MLCT lowest excited state, its relaxation in various media (solvents, ionic liquids and proteins), nonradiative decay to the ground state and its electron-transfer or isomerization reactions. Alongside, we will discuss the structures and characters of the excited states involved, as documented by time-resolved IR spectra and DFT calculations.
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