Molecular design of conjugated polymers for the control of conformation, electronics and self-assembly

The design, synthesis and characterization of organic electronic materials, in particular luminescent conjugated polymers, with structural motifs that allow for the controlled modulation of their photophysical properties are presented. In Chapter 1, the synthesis of new heterocyclic oligo(phenylene) analogues based on soluble, nonaggregating 1,2-diazines is reported. Palladium-catalyzed reductive coupling methods were developed to allow for the preparation of large quantities of iptycene-derived bipyridazines and biphthalazines, and the controlled synthesis of well-defined oligomers up to sexipyridazine. Crystallographic, spectroscopic and computational evidence indicate that in these analogues, hindrance at the ortho position is relaxed relative to poly(phenylene)s, which can favor planarization and extension of conjugation. New poly(aryl ether)s that incorporate iptycene-derived pyridazines have been prepared by three different synthetic routes, including a novel reductive polymerization of poly(aryl alkyl ether)s (Chapter 2). Some of these polymers exhibit low dielectric constants due to the introduction of internal free volume. Iptycene-derived pyridazines were also incorporated in conjugated organic materials that show thermotropic liquid crystalline properties and in platinum-based monomers for conjugated phosphorescent polymers that exhibit high luminescence efficiency under ambient conditions (Chapter 3). The luminescent properties of these platinum complexes are attributed to the introduction of steric bulk that prevents the formation of quenched aggregates. The donor-acceptor strategy to bandgap engineering was applied to the preparation of a highly selective fluorescent probe for thiol bioimaging (Chapter 4), and to the synthesis of conjugated luminescent polymers that incorporate new electron deficient monomers based on 2,1,3-benzothiadiazole and 2,1,3-benzooxazole bearing solubilizing side-chains (Chapter 5).

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2008

Author dc:creator

• Bouffard, Jean, Ph. D. Massachusetts Institute of Technology

Advisor dc:contributor.advisor

• Timothy M. Swager.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/42915

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/42915