The synthesis and characterizations of luminescent cerium(III) complexes with amide, aryloxide, guanidinate and halide ligands will be presented. These well-defined molecular complexes feature various emission colors, such as yellow, green and blue, and distinct photoluminescence properties. Time-dependent density functional theory (TD-DFT) calculations together with natural transition orbitals (NTOs) calculations were applied to assist identification of the long-lived 2D excited state for the cerium(III) complexes. These luminescent cerium(III) complexes were found to be potent reductants in their 2D excited states, allowing for them to mediate organic transformations through single electron transfer. Quenching kinetics of the corresponding metal-centered excited states by organohalides was also explored. Furthermore, stoichiometric and catalytic arylation reactions of benzene and dehalogenation reactions of aryl halides were demonstrated for this new category of molecular photo-reductants and photo-redox catalysts.

Excited-state metalloradicals: Luminescent cerium(III) complexes for photo-redox chemistry

254th National Meeting (2017)

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