Solvent-induced self-assembly of hydrogen bonded P4VP-perylenebisimide comb polymer

Abstract

Polymeric supramolecular assemblies were formed when an unsymmetric perylenebisimide substituted with ethylhexyl chains on one end and functionalized with 3-pentadecylphenol at the other termini (PDP-UPBI) was complexed with poly(4-vinylpyridine) (P4VP) via hydrogen-bonding interaction. The selfassembly behavior of this polymeric supramolecule poly(4-vinylpyridine)-perylenebisimide P4VP(PDP-UPBI) 1.0 was studied in solvents of varying polarity like chloroform (CHCl 3 ) and methylcyclohexane (MCH). Variable concentration and variable temperature proton NMR studies in CDCl 3 and deuterated 1,1,2,2-tetrachloroethane (TCE), respectively, revealed the polymeric nature of the perylenebisimide upon complexation and the high thermal stability of the self organized structures in solution. The improved solubility afforded by the complexation enabled variable temperature UV-Vis absorption studies in the non-polar solvent MCH, which indicated the existence of strong face-to-face stacked H-type aggregates. The strong fluorescence quenching in MCH also supported the identification of the nature of aggregates as co-facial H-type. Although the existence of aggregates was not very evident in dilute solutions of chloroform, the fluorescence of the P4VP(PDP-UPBI) 1.0 was quenched compared to that of PDP-UPBI. Thin spin coated films of the complex from chloroform exhibited features of rotationally displaced H-type aggregates characterized by blue shift of absorption maxima and the appearance of a new red shifted peak at 540 nm with weak aggregate emission beyond 600 nm.Morphology analysis of drop cast samples using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed the formation of micrometer long multilamellar nanofibers from CHCl 3 and two dimensional multilamellar nanosheets upon switching the solvent to MCH.

P4VP and oligo(phenylenevinylene)-perylenebisimide mixed donor-acceptor supramolecular comb polymer complexes with improved charge carrier mobility

“…The aggregation pattern of UPBI‐PDP in thin film exhibited features of both H (blue shifted 0‐0 absorption band) and J (appearance of new red shifted bands around 560 and 580 nm) type aggregates . However, we have attributed it to H type aggregates based on elaborate solution studies involving variable temperature absorption studies etc, which were reported previously …”

“…[37][38][39] However, we have attributed it to H type aggregates based on elaborate solution studies involving variable temperature absorption studies etc, which were reported previously. 40 The absorption spectra of drop cast films of the 100% P4VP complexes of the donor and acceptor as well as that for the mixed D-A complexes are given in the Supporting Information (Supporting Information Fig. S8).…”

Single‐Step Synthesis of Novel Polyionic Liquids Having Antibacterial Activity and Showing π‐Electron Mediated Selectivity in Separation of Aromatics

“…The interaction between the polymers and the solvent molecules basically decides the size of aggregation of the polymer in different media. The aggregation behavior is very important as it decides the surface area as well as surface charge of the polymer ,. By changing the media, the aggregation behavior of the PIL can be fine‐tuned and hence its particular application can also be fine‐tuned.…”

“…The aggregation behavior is very important as it decides the surface area as well as surface charge of the polymer. [50,51] By changing the media, the aggregation behavior of the PIL can be finetuned and hence its particular application can also be finetuned. For the present case laser diffraction technique was employed for the determination of the size of aggregation.…”

Supramolecular complexes of poly(3‐Hexylthiophene)‐block (and random)‐poly[3‐(2‐(6‐carboxyhexyl)methyl)thiophene] copolymers with perylene bisimide

“…All the samples were recorded in CDCl 3 at a concentration of 10 mg/mL. The proton NMR spectra of the complexes showed prominent broadening of the peaks with shifting corresponding to UPBIPy protons, which was more pronounced in RC . This might be due to the higher content of UPBIPy in RC (49% composition of M2 units in P3HT‐ r ‐P3COOH) compared to only 28% composition of COOH bearing M2 units in P3HT‐ b ‐P3COOH.…”