Supramacromolecular chemistry: Self‐assembly of polystyrene‐based multi‐armed pseudorotaxane star polymers from multi‐topic C₆₀ derivatives

Abstract

Multitopic dibenzylammonium derivatives (4) of C60 were prepared by Bingel reactions of C60 with a malonate diester (2) containing two t‐BOC protected dibenzylamine moieties, followed by deprotection and protonation. Self‐assembly of model pseudorotaxanes 5 from the multidibenzylammonium C60 derivatives with dibenzo‐24‐crown‐8 was studied by 1H NMR spectroscopy and mass spectrometry. Self‐assembly of linear and star‐shaped pseudorotaxanes 8 with up to 12 arms based on polystyrenes bearing terminal DB24C8 host units (7) and the guest functionalized C60 salts was demonstrated by 1H NMR spectroscopy and solution phase viscometry. These studies provide further evidence of the potential of supramacromolecular chemistry in construction of complex polymeric architectures. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6472–6495, 2009

Supramolecular polymers constructed by crown ether-based molecular recognition

“…More complicated multi-armed star polymers were derived from multiple pseudorotaxane formation of the multitopic secondary ammonium salt functionalized C 60 and DB24C8-functionalized polystyrene. 68 When the paraquatterminated polymers 55 or 56 and BMP32C10-centered polystyrene 50 were mixed in solution, a three-armed star polymer (Fig. 19, 58d) was formed.…”

A Supramolecular Polymer Blend Containing Two Different Supramolecular Polymers through Self‐Sorting Organization of Two Heteroditopic Monomers

“…Polymer blends have been widely studied in polymer chemistry and materials science,6, 7 and as such supramolecular polymer blends, defined as mixtures of two or more different and mutually exclusive supramolecular polymers, are an attractive topic 3m. There are beautiful examples of miscible polymer blends based on either multiple hydrogen‐bonding,7a,c,d,h π‐stacking,7i carboxy–amine interactions,7j or crown ether functionlized polymers with ammonium‐ or paraquat‐functionalized polymers 7b,e–g. However, these blends were composed of high‐molecular‐weight, conventional covalently bonded polymers instead of noncovalently connected supramolecular polymers 7.…”

Synthesis of Bottlebrush Copolymers Using a Polypseudorotaxane Intermediate

“…Widespread interest in supramolecular polymers and their potential applications has led to the development of novel polymeric architectures analogous to those of conventional macromolecules. Thus, complementary host–guest complexations leading to pseudorotaxanes enable the fabrication of various supramolecular topologies, , including linear polymers, − cyclic polymers, ,, hyperbranched polymers, ,,− star polymers, ,,− dendrimers, ,,, slide-ring materials, ,,, and polymeric networks ,,− …”