| The ultimate goal of the planned research is the development of biomimetic photocatalysts based on widely available metals (Ni and Fe), that will be able to reduce protons and produce H2, and to obtain currently lacking insight into the mechanism behind this process. Novel synthetic inorganic chemistry in combination with supramolecular chemistry will be employed to prepare bioinspired heterobimetallic complexes and their reactivity for photo-induced electron transfer will be evaluated. These endeavors will be coupled with detailed investigation of structural rearrangement processes occurring during the catalytic action, using the recently developed methodology of time-resolved 2D-IR spectroscopy. The combination of synthetic photochemistry dedicated to the problem of sustainable energy-sources with in-depth physical studies will contribute to a more complete understanding of this challenging chemistry. We aim to assemble new heterobimetallic entities based on Ni and Fe that will serve as structural and functional models for the NiFe-hydrogenases active site. Such heterobimetallic dimeric species with the anticipated level of control and sophistication do not exist as yet and as such should spark interest from inter alia the bioinorganic and bio-chemistry communities. Built-in pyridylphosphine ligands will serve as platform for the assembly of suitable photosensitizers that will in effect enable the controlled transfer of electrons from the chromophore into the bimetallic sub-unit. Coupled with sacrificial proton sources, the overall reduction of protons to yield H2 based on solar light as the sole energy source will be achieved on a metal center of unprecedented complexity. |
