RUI - Ferrocene - containing panchromatic BODIPY, azaBODIPY, and porphyrin nanocarbon assemblies for light-harvesting

University Of Minnesota Duluth, Duluth MN

Investigators

Abstract

In this project, Professor Viktor Nemykin of the Department of Chemistry at University of Minnesota Duluth, funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, will develop new classes of ferrocenyl-containing nanocarbon boron-dipyrromethene (BODIPY), azaBODIPY, and porphyrin supramolecular assemblies. The goal of this research is to exploit the characteristics of these donor-acceptor supramolecular superstructures for systems for solar light energy conversion into stored chemical energy or electricity (e.g. organic photovoltaic cells). The project lies at the interface of organic, organometallic, inorganic, materials, and theoretical chemistry, and is thus well designed for the education of undergraduate and graduate (M.S.) scientists. It will also provide excellent education and hands-on experimental training for undergraduate students including members of groups underrepresented in science. This proposal centers on the design and characterization of new panchromatic BODIPYs, azaBODIPYs, and porphyrins connected to redox-active donor (ferrocene) and acceptor (fullerene, carbon nanotube, graphene) centers. The proposed supramolecular assemblies with fullerenes/nanotubes/graphene might be useful for light-harvesting. In the proposed research, BODIPYs, azaBODIPYs, and porphyrins will be used as essentially planar, highly conjugated platforms, which is useful for a long-range metal-metal coupling and effective electron-transfer between redox-active centers. In the planned work, organometallic redox-active centers will be covalently linked to BODIPY, azaBODIPY, or porphyrin core in order to prepare a variety of systems with systematic variation in geometric and electronic structures. These donor-antennae dyads will be further covalently or non-covalently linked to the nanocarbon derivatives such as fullerenes, carbon nanotubes, or graphene. The systematic investigation of proposed compounds will help to understand how and to what extent the nature of the pi-conjugated platform, the through-bond and through-space distance(s) between the redox centers, and the type of donor and acceptor conjugation with the antennae pi-system can control redox processes, stability, and photo-induced electron-transfer properties in these systems. The long-term goals include the fundamental understanding and improvement of a basic knowledge on structure, reactivity, and electronic interactions in complex redox-active porphyrinoid-type supramolecular arrays, the search for aromatic pi-systems useful for applications in molecular electronics, light-harvesting, catalysis, and photocatalysis, and the creation of new methodologies for preparation of porphyrins and their analogues with useful properties.