The functonalization of C60 and C70 by means of a (2+2) photocyclization of cyclic enones onto the fullerene skeleton will be examined. The generality and chemoselectivity of the methodology will be developed through a selective use of different enones, and comparisons of the product distributions obtained with C60 and C70 fullerenes. Mechanistic details will be elucidated with particular attention paid to understanding why the high energy enone triplets prefer to undergo the chemical reaction with the fullerene skeleton, rather than energy transfer to a lower energy fullerene triplet state. Metalloporphyrins tethered to the fullerenes will be achieved by means of this photosynthetic methodology, and the photoinduced electron transfer between the tethered fragments examined. Graduate and undergraduate students will be involved in all aspects of the research including its presentation at scientific meetings. With this award, the Organic and Macromolecular Chemistry Program supports the research and educational activities of Professors Schuster and Wilson of the Department of Chemistry at New York University. Professors Schuster and Wilson will focus their research efforts on generalizing a photochemical methodology for functionalizing C60 and C70 fullerenes. Photophysical experiments will be undertaken to elucidate the mechanism of addition and the factors affecting the rate of chemical reaction with the fullerene skeleton relative to the rate of energy transfer. Professors Schuster and Wilson involve both graduate and undergraduate in all aspects of the work making the research and its presentation educational vehicles.
