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Synthesis of Organic and Water Soluble Poly(1,4-phenylenevinylenes) Containing Carboxyl Groups:  Living Ring-Opening Metathesis Polymerization (ROMP) of 2,3-Dicarboxybarrelenes

Wagaman, Michael W. and Grubbs, Robert H. (1997) Synthesis of Organic and Water Soluble Poly(1,4-phenylenevinylenes) Containing Carboxyl Groups:  Living Ring-Opening Metathesis Polymerization (ROMP) of 2,3-Dicarboxybarrelenes. Macromolecules, 30 (14). pp. 3978-3985. ISSN 0024-9297. https://resolver.caltech.edu/CaltechAUTHORS:20180719-141848634

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Abstract

2,3-Dicarboxybicyclo[2.2.2]octa-2,5,7-triene (barrelene) monomers (4a,b) were synthesized by a novel route and then polymerized by ring-opening metathesis polymerization (ROMP). Complete initiation of the ROMP initiator (5) and living polymerization of monomer 4b were achieved by tuning the activity of 5 with hexafluoro-tert-butanol (HFB) and tetrahydrofuran (THF). The precursor polymers (6a,b) were readily converted to diester-substituted poly(1,4-phenylenevinylenes) (PPVs) (7a,b) by aromatizing the cyclohexadiene rings using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The resulting PPVs were highly luminescent, and polymer 7b, bearing tert-butyl groups on its esters, was soluble in methylene chloride and chloroform. We found that partially oxidizing 6b so that only 80% of the polymer units are aromatized increases both the solubility and photoluminescence quantum yield of 7b. Deprotection of polymer 7b by acid-catalyzed thermolysis of the tert-butyl groups followed by treatment with aqueous base produced a dicarboxylate PPV (9) that is soluble in water. Photoluminescence and UV/visible absorbance measurements show that, in solution, the PPVs synthesized are highly luminescent and blue shifted relative to films of unsubstituted PPV.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/ma9701595DOIArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Additional Information:© 1997 American Chemical Society. Received February 4, 1997; Revised Manuscript Received April 16, 1997. This work was supported by funding from the United States Office of Naval Research and the United States Air Force. We also thank Dr. D. G. H. Ballard and ICI for their gift of cis-3,5-cyclohexadiene-1,2-diol.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)UNSPECIFIED
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Issue or Number:14
Record Number:CaltechAUTHORS:20180719-141848634
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180719-141848634
Official Citation:Synthesis of Organic and Water Soluble Poly(1,4-phenylenevinylenes) Containing Carboxyl Groups:  Living Ring-Opening Metathesis Polymerization (ROMP) of 2,3-Dicarboxybarrelenes Michael W. Wagaman and Robert H. Grubbs Macromolecules 1997 30 (14), 3978-3985 DOI: 10.1021/ma9701595
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:88011
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:19 Jul 2018 21:37
Last Modified:03 Oct 2019 20:02

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