Resonance-Enhanced Two-Photon Absorption and Optical Power Limiting Properties of Three-Dimensional Perylene Bisimide Derivatives

Push-pull organic structures characterized by an intramolecular charge transfer (ICT) process and pi-electron delocalization are potentially interesting luminescent materials. A series of three-dimensional o-carborane-containing perylene bisimide derivatives (PBIs) were synthesized, and their optical properties were systematically investigated to illustrate the stereo effect, especially on the two-photon absorption (2PA) and optical power limiting (OPL) properties. Open-aperture Z-scan curves showed that all four PBIs displayed strong and broad two-photon absorptivities based on the resonance-enhanced phenomenon. The maximum degenerate two-photon absorption cross section (delta(2PA)) increased with the number of PBI substituents. The derivative CB-PBI possessed a delta(2PA) value of similar to 2400 GM at 650 nm, a significant enhancement in comparison with that of the parent PBI (similar to 719 GM), ascribed to the present stereo effect. When the aromatic-donating units changed from naphthyl and pyrenyl to PBI, the generated multidimensional intramolecular charge transfer (ICT) from the aromatic units to the o-carborane cage contributed to the 2PA processes. All of the fluorophores exhibited excellent optical power limiting (OPL) performances as well as a minimum limiting threshold of similar to 4.98 mJ/cm(2) for CB-PBI. These significant results not only allow us to get deep insight into the nature of the fundamental stereo effect and nonlinear optical (NLO) response involved but also guide us toward the design of new multifunctional luminescent materials.

Automated summary

The synthesis of a series of PBIs revealed their strong two-photon absorption and excellent optical power limiting properties, with CB-PBI showing the lowest limiting threshold. The stereo effect was found to play a significant role in influencing these properties.