Electron and energy transfer systems

We investigate the influence of the core metal ion and axial ligands on photophysical and photochemical processes in the metallocorroles, and corrole donor-acceptor complexes. The focus will be on metallocorroles with Al(III), Ga(III), Sb(III), or Sb(V) as the central metal ion, covering the range from light to fairly heavy metal ions, and allowing the study of the influence of the oxidation state. The kinetics and structural dynamics of newly synthesized metallocorroles will be characterized, from femtosecond to millisecond timescales, using polarization-resolved femtosecond visible and infrared spectroscopy, nanosecond electron paramagnetic resonance (EPR), and laser flash photolysis. The impact of the core metal ion, and its oxidation state, on the 3-dimensional structure of the various electronic states, and the efficiency of the triplet generation, will be studied. The results on isolated metallocorroles will be implemented in studies of electron and energy transfer in corrole based donor- acceptor complexes. Particular emphasis will be devoted to the dependence of the electron and energy transfer on the donor-acceptor distance, their mutual orientation, and the nature of their linkage such as covalent, electrostatic, coordinative, and hydrogen bonding. The information gained will enhance the development of advanced catalytic processes and the design of efficient biomimetic systems.