Electronic transitions of lanthanide cations have characteristics that have found utility in diverse areas including as bioprobes and phosphors. Such 4f-4f transitions are characterized by their weakness, narrow linewidths and long lifetimes. These characteristics all derive from the parity forbidden, core-like nature of the 4f-4f transitions. Cerium is an unusual lanthanide element in that its +3 cation has interconfigurational electronic transitions that can appear in the visible range. In fact, the luminescent characteristics of cerium compounds in the solid state, used in phosphors, derive uniquely from 4f-5d electronic transitions. We have recently demonstrated that visible light provides a useful vehicle to interrogate and develop Ce(III/IV) redox cycling through associated photoredox processes, a new direction in lanthanide chemistry. This work necessitated study of the photophysics of the 4f-5d electronic transitions of molecular cerium complexes. Ultimately, we demonstrated that cerium photoredox cycling can be developed for chemistry on organic substrates. The unique capabilities of cerium luminophores, and their comparison with traditional inorganic triplet photosensitizers, will be discussed.<br/>

Interconfigurational electronic transitions of cerium(III) complexes: Photophysics and photochemistry

254th National Meeting (2017)

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