Chiral substituent containing perylene monoanhydride monoimide and its highly soluble symmetrical diimide: synthesis, photophysics and electrochemistry from dilute solution to solid state

Abstract

A new chiral perylene monoanhydride monoimide (1) with a sterically hindered chiral amine was successfully synthesized for further selective functionalization at terminal positions. At the same time, the chiral perylene diimide (2) with the same amine has been synthesized. The synthesized products were characterized using the data from NMR, IR, MS, UV-vis, DSC, TGA, elemental analysis and cyclic and square wave voltammetry. Compound 2 shows an excellent solubility of 200 mg mL(-1) in chloroform. The band gap energy (Eg), LUMO and HOMO energy values were 2.28, -3.77 and -6.05 eV for 2, respectively in chloroform. In solid state, the band gap energy (Eg), LUMO and HOMO energy values were 1.96, -4.22 and -6.18 eV for 1 and 1.92, -4.13 and -6.05 eV for 2, respectively. Whereas 1 (solid state: -0.58 and -0.69 V vs. ferrocene/ferrocenium couple) and 2 (in chloroform: -1.03 and -1.22 V vs. ferrocene/ferrocenium couple) show two reversible reduction steps, 2 exhibits only one reversible wave (solid state: -0.67 V vs. ferrocene/ferrocenium couple). The diffusion coefficients were determined as 1.91 x 10(-7) and 8.47 x 10(-7) cm2 s(-1) for 1 and 2 in solid state, respectively, and 1.27 x 10(-5) cm2 s(-1) for 2 in solution. The solid state emission ability of the chiral products ( is much more emissive than ) remains a challenge for photonic, electronic and sensor applications. 1 and 2 showed high thermal stability. Efficient prevention of intermolecular pi-pi contacts of fluorophores results in an excellent fluorescence emission in solid state and solubility for 2.

Auxetic springs for seating

“…Furthermore, the enhanced solubility could be attributed to the presence of secondary carbon atoms next to nitrogen atoms, forcing the methyl and phenyl substituents out of the plane of the molecule and thereby hampering the face-to-face π -π stacking of the perylene bisimides. 12 The sterically hindered chiral substituent decreased the short π − π contacts of the chromophores to a certain extent and therefore increased the solubility.…”

“…Strong fluorescence in the solid state could be achieved with the elimination of this self-quenching. 12 The solid-state emission of LPPDI was taken successfully. The chiral asymmetric perylene dye showed excimer-like emission in red light (λ em = 658 nm, with a full width at half maximum of 66 cm −1 ), which was very similar to the excimer-like emissions usually observed for weakly interacting π -stacked perylene molecules in solution.…”

“…The high optical activity compared to N,N -bis((S)-(-)-1-phenylethyl)-3,4,9,10-perylenebis(dicarboximide) is attributed to the asymmetric molecule. 12 The n-π * transitions due to hydrogen bonding inter-actions are electrically forbidden but magnetically permitted; therefore, in the asymmetric molecule, such a transition can have very low absorption of light but high optical activity. Figure 7 shows the CD spectra of LP-PDI in trifluoroacetic acid.…”

Perylene diimide: Synthesis, fabrication and temperature dependent electrical characterization of heterojunction with p-silicon

“…The mixture was, then, cooled to room temperature and the precipitates were isolated by filtration and washed with hot water to obtain dark red powder of monopotassium salt of perylene-3,4,9,10-tetracarboxyllicacid mono anhydride (2) (1.86 g). By making little modification in the procedure reported in the literature [29,30], monopotassium salt of perylene-3,4,9,10-tetracarboxyllicacid mono anhydride (2) (1.86 g) was added to the mixture of n-butylamine (1.26 g, 0.02 mol) in 25 ml of water. The contents were stirred first at room temperature for one hour and then at 363 K for another hour.…”

Novel nanosized water soluble fluorescent micelles with embedded perylene diimide fluorophores for potential biomedical applications: Cell permeability, localization and cytotoxicity

“…Due to their unique properties PDI chromophores could be successfully applied in biological environment as high-performance fluorescent labels. The serious drawback of most of the synthetic dyes for their processing and material science applications is their low solubility in the common solvents and aqueous media [18,19]. Usually the solubility can be improved with the long-tail or swallow-tail conformation that is obtained by long alkyl substitutions in N-position of the dye [20][21][22].…”