RUI - Organometallic Porphyrins, BODIPY, and their analogues for light-harvesting and molecular electronics

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In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Viktor N. Nemykin of the Department of Chemistry and Biochemistry at University of Minnesota Duluth (UMD) will prepare and characterize donor-acceptor dyads and donor-antennae-acceptor triads of organometallic porphyrins and the other aromatic macrocyclic analogues. Professor Nemykin and other research groups have recently shown that introduction of the organometallic substituents into porphyrin cores results in long-range metal-metal coupling properties, which are essential for application of such compounds in molecular electronics and in random access memory devices. It was also shown that organometallic donor-acceptor dyads and donor-antennae-acceptor triads can be used as active components for effective light-harvesting in dye sensitized solar cells and organic photovoltaics. Therefore, this project potentially could result in the preparation of efficient modules for molecular electronics. UMD is a predominantly undergraduate institution and thus the broader impacts include the training of undergraduate as well as graduate (M.S.) students. The project also contributes to the building of an excellent undergraduate and graduate (M.S.) chemistry program at UMD. Organometallics, in particular ferrocene-containing porphyrins and their analogues, display a rich redox and photophysical properties. Redox-driven and/or photoinduced electron- or energy-transfer properties of these systems can be tuned up by modification of the macrocyclic core or by substituents at the ferrocene group. The proposed research will explore synthetic pathways for the preparation of a variety of ferrocene-containing donor-acceptor dyads and donor-antennae-acceptor triads, which could be potentially used in molecular electronics and light-harvesting. A systematic investigation of the proposed compounds will allow the investigators to understand how and to what extent oxidation potentials, stability, as well as photoinduced electron- or energy-transfer properties can be controlled. The factors to be examined include the nature of the central metal ion, through-bond and potentially through-space distance(s) between the transition-metal centers, the geometry (i.e. axial versus equatorial coordination), and the electronic properties of the macrocyclic ligand.