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Synthesis and Arm Dissociation in Molecular Stars with a Spoked Wheel Core and Bottlebrush Arms

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Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States
§ Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn, Germany
Cite this: J. Am. Chem. Soc. 2014, 136, 36, 12762–12770
Publication Date (Web):August 18, 2014
https://doi.org/10.1021/ja506780y
Copyright © 2014 American Chemical Society
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Abstract

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Unique star-like polymeric architectures composed of bottlebrush arms and a molecular spoked wheel (MSW) core were prepared by atom transfer radical polymerization (ATRP). A hexahydroxy-functionalized MSW (MSW6-OH) was synthesized and converted into a six-fold ATRP initiator (MSW6-Br). Linear chain arms were grafted from MSW6-Br and subsequently functionalized with ATRP moieties to form six-arm macroinitiators. Grafting of side chains from the macroinitiators yielded four different star-shaped bottlebrushes with varying lengths of arms and side chains, i.e., (450-g-20)6, (450-g-40)6, (300-g-60)6, and (300-g-150)6. Gel permeation chromatography analysis and molecular imaging by atomic force microscopy confirmed the formation of well-defined macromolecules with narrow molecular weight distributions. Upon adsorption to an aqueous substrate, the bottlebrush arms underwent prompt dissociation from the MSW core, followed by scission of covalent bonds in the bottlebrush backbones. The preferential cleavage of the arms is attributed to strong steric repulsion between bottlebrushes at the MSW branching center. Star-shaped macroinitiators may undergo aggregation which can be prevented by sonication.

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Detailed synthesis and characterization of the initiator, MSW6-Br, and all its precursors; discussion and characterization of the aggregation of (450-Br)6; and distribution of number of arms in star-shaped objects. This material is available free of charge via the Internet at http://pubs.acs.org.

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