Synthesis of well‐defined side chain fullerene polymers and study of their self‐aggregation behaviors

Abstract

Monoalkynyl‐functionalized fullerene was precisely synthesized starting with pristine fullerene (C60) and characterized by multiple techniques. Methyl methacrylate and 6‐azido hexyl methacrylate were then randomly copolymerized via reversible addition fragmentation chain transfer polymerization to build polymer backbones with well‐controlled molecular weights and copolymer compositions. Finally, these two moieties were covalently assembled into a series of well‐defined side chain fullerene polymers (SFPs) via the copper‐mediated click reaction which was verified by Fourier transform infrared spectroscopy and 1H NMR. The fullerene loadings of the resultant polymers were estimated by thermogravimetric analysis and UV–vis spectroscopy, demonstrating consistent and high conversions in most of the samples. The morphology studies of the SFPs were performed both in solution and on solid substrates. Very intriguing self‐aggregation behaviors were detected by both gel permeation chromatography and dynamic light scattering analyses. Furthermore, the scanning electron microscopic images of these polymers showed the formation of various supramolecular nanoparticle assemblies and crystalline‐like clusters depending on the fullerene contents and polymer chain lengths. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3572–3582

Self-Assembly of Monodisperse versus Bidisperse Polymer-Grafted Nanoparticles

“…In contrast, the monomodal PS coated particles have much stronger core–core attractions and thus are much more easily kinetically trapped once they touch each other. Interestingly, similar microscale string-like NP assemblies were previously observed in side chain fullerene polymers . However, the underlying physics responsible for the formation of these interesting NP morphologies is still not clear.…”

“…Interestingly, similar microscale string-like NP assemblies were previously observed in side chain fullerene polymers. 29 However, the underlying physics responsible for the formation of these interesting NP morphologies is still not clear. Current efforts (both experiments and simulations) are in progress to understand the general mechanisms for these more complex self-assembly processes.…”

Convenient syntheses of fullerynes for ‘clicking’ into fullerene polymers

“…Fullerynes were synthesized in one step from C 60 with high yield by reacting terminal-alkyne-functionalized malonates with fullerene via Bingel reaction (Scheme 1 ). The synthesis of mono-alkyne-functionalized malonate could be achieved by reacting alcohol with Meldrum’s acid as reported in literature [ 32,48 ] or the selective hydrolysis of diethylmalonate. [ 47 ] Acid 1 was synthesized as described in literature [ 47 ] and then reacted with 3-butyn-1-ol using Steglich esterification to afford ethyl-3-butyn-1-yl malonate ( 2 ) in a yield of 27.7%.…”

Synthesis and Preliminary Characterization of a PPE-Type Polymer Containing Substituted Fullerenes and Transition Metal Ligation Sites

“…Unlike other studies that show a loss of emission upon aggregation [52], the large size of the fullerenes and their relative isolation from the polymer backbone electronics allow them to effectively buffer the polymer from any interchain deactivation effects. A recent report by Li and Benicewicz [28] suggests that polymers with pendant fullerenes aggregate readily, so our anisotropy results are not surprising. However, we are not aware of such a derivatized polymer insulating the core system from interchain energy transfer deactivation.…”