Abstract

The development of organic photonics and electronics has fueled the need for stable chromophores that can undergo photoinduced electron transfer reactions to yield stable radical ion intermediates. Derivatives of perylene-3,4:9,10-bis(dicarboximide) (PDI) and perylene-3,4-dicarboximide (PMI) are especially intriguing because they show exceptional chemical and photochemical stability. These molecules and their derivatives have been used as building blocks for molecular switches, wires, and logic gates, as well as organic light-emitting diodes, light-harvesting arrays, photorefractive thin films, and solar cells. Much of this work has benefited greatly from the distinct electronic absorption spectra that the radical ions of these molecules exhibit, and their ability to self-assemble into extended structures. The former makes it possible to easily identify these radical ion intermediates in complex electron transfer reactions, while the latter offers the possibility of self-assembling photofunctional materials. The photophysical and redox properties of these molecules can be manipulated by functionalizing the perylene core with electron donating and accepting functional groups. For example, substitution of the 1,7-positions of PDI, or the 9-position of PMI with N-cycloalkylamines, such as N-pyrrolidine, produces chromophores in which the lowest energy electronic transition acquires significant charge transfer character and moves to substantially longer wavelengths relative to those of PMI or PDI. Moreover, the one-electron oxidation potentials become significantly less positive, making these derivatives excellent electron donors in donor-acceptor materials. Substitution of the corresponding positions with cyano groups leads to the cyanated chromophores CN2PDI, CNPMI, and CN3PMI. These molecules are powerful, yet stable, photochemical oxidants for use in novel photonic and electronic materials. Liquid crystalline derivatives of 1,7-cyano and 1,7-bis(N-pyrrolidinyl)PDI self-assemble into ordered structures.

© 2003 Optical Society of America

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