Supramolecular Assembly of Perylene Bisimide with β‐Cyclodextrin Grafts as a Solid‐State Fluorescence Sensor for Vapor Detection

Abstract

A nanoscopic supramolecular aggregate is constructed from perylene bisimide‐bridged bis‐(permethyl‐β‐cyclodextrins) 1 via π–π stacking interactions. Its self‐assembly behavior in organic and aqueous solutions is investigated by UV–Vis, fluorescence, and 1H NMR spectroscopy. Transmission electron microscopy and scanning electron microscopy images show the 1D nanorod aggregation of 1, which is birefringent under crossed polarizer conditions and strongly fluorescent as depicted in the fluorescence microscopy image. X‐ray powder diffraction measurements indicate that 1 forms a well‐ordered crystalline arrangement with a π–π stacking distance of 4.02 Å. Furthermore, the solid‐state fluorescence sensing is explored by utilizing the poly(vinylidene fluoride) membrane‐embedded 1, giving that 1, as a novel vapor detecting material, can probe several kinds of volatile organic compounds and, especially, exhibits high sensitivity to organic amines.

Influence of Molecular Aggregation on Electron Transfer at the Perylene Diimide/Indium-Tin Oxide Interface

“…Comparing the spectra in Figure 3A to the solution spectra shows that immobilization on ITO produced significant spectral changes, including band broadening, hypsochromic shifts, and decreases in the 0-0/0-1 band ratios, all of which are indicative of H-aggregate formation. 45,50,51 Although aggregation is evident in all four film types, the degree varied. As increasingly bulky substituents were added to the PDI core, the vibronic bands became narrower and better resolved, and the 0-0 band became more prominent.…”

“…488 nm) vibronic bands within the S 0 -S 1 manifold. [44][45][46][47] A 0-0/0-1 band ratio close to 1.6 is considered to be monomeric. 45,48,49 Here a 0-0/0-1 band ratio of 1.6 was measured for all four PDI-PAs when dissolved in the solvents from which they were adsorbed to ITO ( Figure S3 in SI), indicating they are essentially fully monomeric prior to film formation.…”

“…[44][45][46][47] A 0-0/0-1 band ratio close to 1.6 is considered to be monomeric. 45,48,49 Here a 0-0/0-1 band ratio of 1.6 was measured for all four PDI-PAs when dissolved in the solvents from which they were adsorbed to ITO ( Figure S3 in SI), indicating they are essentially fully monomeric prior to film formation. Comparing the spectra in Figure 3A to the solution spectra shows that immobilization on ITO produced significant spectral changes, including band broadening, hypsochromic shifts, and decreases in the 0-0/0-1 band ratios, all of which are indicative of H-aggregate formation.…”

Novel EDTA-ligands containing an integral perylene bisimide (PBI) core as an optical reporter unit

“…Therefore, several attempts have been performed in order to increase their solubility in aqueous media, either with functionalization in the bay region [12][13][14][15][16] or at the side imide groups. [17][18][19][20][21][22][23][24][25] Recently, we have introduced a series of highly water-soluble PBIs containing anionic (R 1 ) or cationic (R 2 ) Newkome dendronized substituents -representative examples are given in Fig. 1.…”

Photoinduced Interactions in a Pyrene-Calix[4]arene-Perylene Bisimide Dye System: Probing Ground-State Conformations with Excited-State Dynamics of Charge Separation and Recombination

“…4 Examples of supramolecular recognition and organization applied in materials science are represented by hydrogen-bonded polymer systems 5 as well as cyclodextrin-functionalized fabrics 6 and dyes. 7 The selforganization can, in principle, be attained by introduction of a supramolecular unit that can be used to induce a secondary structure.…”