Perylenediimides are ideal candidates for the substitution of fullerene derivatives as electron acceptors in bulk heterojunction organic solar cells due to their extremely intense light absorbance, high electron mobility and excellent photochemical stability.

Perylenediimide (PDI) dyes dispersed in polymer films have demonstrated great success as active materials in thin film organic lasers (TFOLs). The type of matrix used to host the dye and the dye doping rate are both crucial parameters to optimize laser performance. This work reports the study of two soluble PDIs, the comercial derivative perylene orange (PDI-O) emitting at around 580 nm , and a new dye (b-PDI-A) with subsituents at the 1,7 bay positions of the PDI core emitting at around 620 nm , dispersed at different doping levels (up to 8 wt% and 50 wt%, for PDI-O and b-PDI-A, respectively) in two widely used polymers for optoelectronics polystyrene (PS) and poly(methyl methacrylate) (PMMA). The main goal is to determine which of these two polymers, and at which dye concentration, provides the best results for their use in TFOLs. The assessment of the active materials has been carried out through the analysis of their absorption, photoluminescence and amplified spontaneous emission (ASE) properties. Their capability to form high quality optical waveguides has also been studied by determining gain coefficients and waveguide losses. Results have shown that for both types of PDI derivatives PS is better than PMMA at any concentration, that means larger photoluminescence efficiency, lower ASE thresholds, longer ASE operational lifetimes, larger gain and lower propagation waveguide losses. In addition, the onset concentration at which dye aggregation becomes significant as to negatively affect the optical properties is lower in PMMA than in PS, thus the larger the blending ratio, the larger the superiority of PS with respect to PMMA.

The most recent advances in the incorporation of perylenediimides in photovoltaic devices are highlighted.

Directly linked to promote strong intramolecular interactions, donor–acceptor dyads and a donor–acceptor–donor triad featuring zinc phthalocyanine (ZnPc) as electron donor and perylenediimide (PDI) as electron acceptor have been synthesized and characterized. Owing to complementary absorption features of the entities, improved light absorption was witnessed in these conjugates. The optimized geometry and electronic structures showed the majority of the highest occupied molecular orbital (HOMO) on the ZnPc entity, whereas the lowest unoccupied molecular orbital (LUMO) was on the PDI entity, suggesting that the charge‐separated states would be ZnPc+–PDI.−. The electrochemical and free‐energy calculations suggested exothermic energy and/or electron transfer processes via the singlet states of PDI or ZnPc entities depending on the excitation wavelength of the laser used. The measured rates using femtosecond pump‐probe spectroscopy coupled with global analysis of transient data revealed ultrafast energy transfer from 1PDI* to ZnPc followed by charge separation. However, when ZnPc was selectively excited, only electron transfer was witnessed wherein the time constants for forward and reverse electron transfer processes followed Marcus predictions. The absorption in a wide section of the solar spectrum and the ultrafast charge separation suggest the usefulness of these systems as good photosynthetic models.

(Un)substituted perylenediimides react with (un)functionalized benzynes yielding core-expanded diimides.

The presence of fluoride ions in the reaction of chloro- or bromo-PDIs with alcohols and thiols leads to a spectacular increase in the yields of substituted compounds.

Polymer waveguides doped with luminescent materials serve as a suitable flexible platform for active elements (lasers and amplifiers) in on-chip optical circuits. However, at present, the best parameters (lowest thresholds) achieved with these devices are obtained with the use of the stripe excitation technique in the framework of which external illumination of an active material along the whole length of the waveguide is realized that is not convenient for the waveguide on-chip integration and requires high peak energies due to the large excitation area. In the present work, an elegant method is proposed to overcome this obstacle and provide efficient active material pumping along the whole waveguide length with use of on-chip integration compatible edge-type excitation light injection. This novel type of planar active-passive polymer waveguides includes a thin (50–100 nm) active layer of poly­(methyl methacrylate) (PMMA), which is heavily doped with highly luminescent perylenediimide (PDI) molecules, sandwiched between two cladding (passive) PMMA layers. This structure efficiently exploits the excellent light-emitting properties of PDIs with a confinement of both the excitation beam and the photoluminescence in the active PMMA–PDI film. In this way, the absence of losses in the PMMA claddings guarantees the propagation of the pump beam along the whole length of the structure (≈1 mm) in order to provide the required excitation to obtain stimulated emission. Geometrical parameters are optimized to demonstrate the amplified spontaneous emission with a threshold as low as 0.9 μJ and a line width as narrow as 2 nm.

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