Supramolecular Depolymerization in the Mixture of Two Poor Solvents: Mechanistic Insights and Modulation of Supramolecular Polymerization of Ionic π‐Systems

Abstract

Solvents are fundamentally essential for the synthesis and processing of soft materials.S upramolecular polymers (SPs), an emerging class of soft materials,are usually stable in single and mixtures of poor solvents.I nc ontrast to these preconceived notions,h ere we report the depolymerization of SPs in the mixture of two poor solvents.T his surprising behavior was observed for well-known cationic perylene diimides (cPDIs)i nt he mixtures of water and amphiphilic organic solvents such as isopropanol (IPA). cPDIs form stable SPs in water and IPAbut readily depolymerize into monomers in 50-70 vol% IPAcontaining water.This is due to the selective solvation of the p-surface of cPDIs by alkylchains of IPAand ionic side chains by water,asevidenced by molecular dynamic simulations.M oreover,b ys ystematically changing the ratio between water and amphiphilic organic solvent, we could achieve an unprecedented supramolecular polymerization both by increasing and decreasing the solvent polarity.

Controlling the length of porphyrin supramolecular polymers via coupled equilibria and dilution-induced supramolecular polymerization

“…Here not only the homo-interactions between monomers must be considered, but also the hetero-interactions between all components over a wide range of conditions such as temperature, composition, solvent, and concentration. A number of elegant examples demonstrate selectivity of one pathway over the other by small changes in the solvent composition 16 – 19 . The group of Aida reported on thermally bisignate polymerization of porphyrin monomers by tuning the interactions between an alcohol associating with the monomers over a wide range of temperatures 20 , 21 .…”

Synthesis and Self‐assembly of Benzoperylene Benzimidazoles: Tunable Morphology with Aggregation‐Induced Enhanced Emission

“…The fluorescence quantum yield of BPBI-1 (ϕ MCH = 1%) in 100% MCH is nearly 8 times higher than in pure CHCl 3 (ϕ CHCl3 = 0.12%) (Figure S11). [17] These observations clearly indicate the AIEE nature of BPBI-1 which is further evident from the photograph of its solutions in CHCl 3 -MCH mixtures under 365 nm UV light (Figure 2c). Due to the AIEE behaviour, BPBI-1 shows bright-red fluorescence in the powder and thin-film states as well (Figure 2d).…”

“…First, perylene is treated with excess of maleic anhydride and p-chloranil at 240 °C for 13 min to result benzoperylene anhydride (3) in quantitative yield. [17,19] Next, the condensation of 3 with dialkoxy orthodiamines in quinoline at 200-230 °C for 14 h resulted BPBIs in good yields (see Supporting Information). [20] BPBIs were characterized by 1 H and 13 C-NMR spectroscopies, highresolution mass spectrometry, infrared spectroscopy and melting point (see Supporting Information).…”

“…[16] We have very recently reported the self-assembly of cationic BPI in water and amphiphilic organic solvents. [17] To synthesize more rigid πsystem of benzoperylene with extended conjugation, we have coupled it with benzimidazole linkage. The resultant BPBIs shows absorption up to 600 nm whereas the emission till NIR regions (~800 nm) due to the presence of donor and acceptor functional groups.…”

Giant spin pumping at the ferromagnet (permalloy) – organic semiconductor (perylene diimide) interface

“…38,39 Moreover, the optoelectronic properties and supramolecular organization of PDIs can be readily tuned by chemical functionalization at the imide positions and pconjugated core. [40][41][42][43] As a result, PDIs are emerged as an alternative to fullerenes and led to the development of fullerene-free solar cells. [44][45][46] Moreover, PDIs and their supramolecular materials are widely explored as active components in OFETs, uorescence spectroscopy, energy storage devices and sensors [47][48][49][50][51] Despite these novel features, to the best of our knowledge, so far PDIs are not explored in spintronic devices.…”