Characterization of novel perylene diimides containing aromatic amino acid side chains

Abstract

Perylene diimide derivatives have attracted initial interest as industrial dyes. Recently, much attention has been focused on their strong π–π stacks resulting from the large PDI aromatic core. These PDI stacks have distinct optical properties, and provide informative models that could mimic light-harvesting systems and initial charge transfer typical of photosynthetic systems. The absorption property of PDI derivatives may be tuned from visible to near-infrared region by peripheral substitution. We have studied a new class of PDI derivatives with aryl substituents derived from the side chains of aromatic aminoacids (Tyrosine, Tryptophan and Phenylalanine). We have investigated their absorption and the fluorescence properties in a set of organic solvents and established their different tendencies to aggregate in solution despite their solubility. Most aggregation appears to be unordered. One PDI analogue (the one formed from Tyr) in Methanol, however, appears to form J-type aggregates. Based on our results the compounds appear to be promising for future investigations regarding the interaction of these dyes with biomolecules.

Improving the Quantum Yields of Perylene Diimide Aggregates by Increasing Molecular Hydrophobicity in Polar Media

“…Although morphology control has been studied for a variety of PDI systems, many of the approaches used to control aggregation have been performed in halogenated or organic solvents. There has been an increasing interest in creating PDIs that are soluble in aqueous or more polar solvents . Many of these molecules use hydroxy‐terminated, large dendritic or oligosilsesquioxane groups to deter aggregation and dimerization of the PDIs in these solutions.…”

“…[12,13] The aggregate morphology andc rystal structure can also be controlled. [14][15][16][17][18][19][20][21][22] PDIs can interactt oc reate chiral or helical structures, [23] wires, [20,24] "fish-tail" structures, [25] liquid crystal phases, [26] self-assembled mixed aggregates, [27][28][29] and crystallites of varying degrees of disorder. [30,31] These molecular morphologyand electronic modificationshave facilitated many potential materials applications.…”

“…[2,17,[32][33][34] Although morphology control has been studied for av ariety of PDI systems, many of the approaches used to control aggregation have been performed in halogenated or organic solvents.T here has been an increasing interest in creating PDIs that are soluble in aqueous or more polar solvents. [18,19,[35][36][37][38][39][40] Many of these molecules use hydroxy-terminated, large dendritic [41] or oligosilsesquioxane [42][43][44] groups to deter aggregation and dimerization of the PDIs in these solutions. The use of less toxic mediai np roducing optoelectronic devices, such as plastic solarc ells, would improve the overall fabrication capabilities of these systems.…”

Optoelectronically active luminescent valine‐substituted perylene diimide: structure‐property correlation via spectroscopic and density functional approaches

“…The different aminoacids that have been employed for synthesizing water-soluble PDIs are particularly glycine, alanine, phenylalanine, leucine, methionine, tyrosine, lysine, and aspartic acid. [11][12][13] Roy et al synthesized PDI-tyrosinebased hydrogelator which was found to exhibit excellent photo-switching behavior with a high photoresponse value within the pH range 5.00 to 9.00. [14] Schmidt et al synthesized alanine/lysine-based chiral, water-soluble PDI derivatives and studied the circular dichroic effects in buffer solution and its aggregation behavior having interesting aggregation properties.…”

Fluorescent Polymer—Single‐Walled Carbon Nanotube Complexes with Charged and Noncharged Dendronized Perylene Bisimides for Bioimaging Studies

“…They have been versatilely employed as fluorescent labels, membrane markers, or anti‐inflammatory agents . The striking photostability of PBI expressed in long fluorescence lifetimes of ≈4–5 ns and monoexponential fluorescence decays over at least 16 ns becomes obvious in comparison to other conventional fluorescent probes such as cy5 (0.91 ns), alexa fluor 647 (1.04 ns), and rhodamine B (1.74 ns) with significantly lower lifetimes. The superior long‐term photostability of PBIs compared to common fluorophores like coumarin or fluorescein was recently demonstrated in a study by Zimmerman and co‐workers; additionally, they were able to improve the FQYs of PBIs by site‐isolation of the fluorophore in the imide positions.…”