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Article

Syntheses and Model Complexation Studies of Well-Defined Crown Terminated Polymers

Supporting Info

Harry W. Gibson,*^† Zhongxin Ge,^† Feihe Huang,^† Jason W. Jones,^†^‡ Hervé Lefebvre,^†^§ Matthew J. Vergne, and David M. Hercules

Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061, and Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235

Macromolecules, 2005, 38 (7), pp 2626–2637

DOI: 10.1021/ma047811y

Publication Date (Web): February 22, 2005

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

†

Virginia Polytechnic Institute and State University.

‡

Present address: E. I. duPont de Nemours and Company, Jackson Laboratory, Deepwater, NJ 08023.

Present address: Laboratoire de Synthese Macromoleculaire-UMR 7610 4, Université Pierre & Marie Curie, Place Jussieu/boite 184 75252 Paris, Cedex 05, France.

‖

Vanderbilt University.

Abstract

A TEMPO-based free radical initiator (4a) containing a dibenzo-24-crown-8 (DB24C8, 2a) moiety was synthesized. A similar initiator (4b) based on bis(m-phenylene)-32-crown-10 (BMP32C10, 1b) was also synthesized. The crown-based initiators were used to prepare crown ether terminated polystyrenes of narrow molecular weight distribution (PDI). The DB24C8-terminated polymer 5 was demonstrated to form a pseudorotaxane complex (18) with dibenzylammonium hexafluorophosphate (17), but because of its small cavity, 5 cannot complex bulky N,N‘-dialkyl-4,4‘-bipyridinium (paraquat or viologen) salts. On the other hand, the BMP32C10-terminated polymer 11 complexed N,N‘-bis(p-tert-butylbenzyl)-4,4‘-pyridinium bis(hexafluorophosphate (paraquat salt, 23) strongly, but did not interact with dibenzylammonium hexafluorophosphate (17) to a detectable extent. Therefore, these new polymeric hosts are capable macromolecular building blocks for supramacromolecular chemistry using pseudorotaxane complexation, and furthermore, both show selectivity; the DB24C8 polymer is selective for secondary ammonium ion complexation, and the BMP32C20 polymer is highly selective for paraquat recognition. Future work will involve application of these new functional polymers to preparation of star, graft, and block structures by self-assembly.