Design and synthesis of conjugated macrocycles and polymers

The design, synthesis and characterization of conjugated macrocycles and polymers are presented in this dissertation. In particular, work involving the exploration of unusual and/or novel aromatic structures for various materials applications is described in detail, along with appropriate discussions of relevant structure-property relationships. A brief general introduction to J-aggregates and conjugated polymers is given in Chapter 1, which represents two major areas that are dealt with throughout this thesis. Besides providing an overview of the basic principles, this introductory chapter will hopefully serve to give insight into the motivation behind the work discussed herein. In Chapter 2, the facile one-step construction of highly functionalized cyclohexa-mphenylene macrocycles from simple monobenzenoid building blocks is presented. This methodology is based on a six-fold Suzuki-Miyaura coupling, and represents an improvement over preceding cyclohexa-m-phenylene preparations. In Chapter 3, the development of novel J-aggregating dibenz[aj]anthracene-based macrocycles are reported. These materials are uniquely non-polar compared to all other known Jaggregates, and are also much more photostable relative to the classic J-aggregating cyanine dyes. A variation on the dibenzanthracene theme was extended to the work described in Chapter 4, which features poly(aryleneethynylene)s containing dibenz[a,h]anthracene repeat units. These polymers have unusual stair-stepped structures that confer unto them spectroscopic properties that are atypical of the more common poly(phenyleneethynylene)s. Chapter 5 details recent efforts aimed at utilizing the J-aggregate design principles discussed in Chapter 3 in our search for new J-aggregate candidates in various conjugated polymers and small molecules (e.g. the dibenz[a,m]rubicenes).

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2010

Author dc:creator

• Chan, Julian M. W. (Julian Mun Weng)

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/1721.1/57894

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/57894