π-Conjugated (co)polymers are an important class of organic semiconducting materials for (opto)electronic device applications such as organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and organic solar cells. The semiconducting capabilities of these materials are a result of π-electron delocalization along the (co)polymer backbone. In additional to their desirable electrical and optical properties, these materials must also exhibit atmospheric stability and solution processability, hence polyenes such as polyacetylene have no commercial viability despite their high electrical conductivity. Therefore, polyaromatics are the preferred materials despite resonance effects that confine π-electrons to individual aromatic scaffolds and inhibit optimal charge-carrier delocalization along the polymer chain. Recently, there has been interest in preparing π-conjugated polymers that feature both the favorable conjugation lengths typical of polyenes (e.g., polyacetylene) and the atmospheric stability and processability typical of polyaromatics (e.g., polythiophene). Unfortunately, there remains a synthetic challenge to prepare non-aromatic π-conjugated precursors that can be readily incorporated into π-conjugated polymeric systems. The work described herein addresses this challenge by investigating the viability of using 5,5-dimethylcyclopentadiene as a non-aromatic building block with the topology of common aromatics such as thiophene, furan, and pyrrole. Specifically, a series of cyclopentadiene-containing (macro)molecules were prepared by Suzuki-Miyaura cross-coupling reaction and their structural, spectroscopic, and electrochemical properties characterized by 1 H NMR, single crystal X-ray crystallography, cyclic voltammetry, and/or UV/vis absorption and fluorescence spectroscopies. The results of our investigation show that the cyclopentadiene moiety tends to reduce optical band-gap and onset oxidation potentials in the majority of systems studied here. Moreover, OLEDs and OFETs devices employing Cp-containing (macro)molecules have been prepared in collaboration with the Carroll and Heeney groups at Wake Forest University and Imperial College-London respectively. To the best of our knowledge, these are the first examples of (opto)electronic devices employing cyclopentadiene-based π-conjugated materials.
Subject (authority = RUETD)
Topic
Chemistry
Subject (authority = ETD-LCSH)
Topic
Polymers
RelatedItem (type = host)
TitleInfo
Title
Rutgers University Electronic Theses and Dissertations
Identifier (type = RULIB)
ETD
Identifier
ETD_7441
PhysicalDescription
Form (authority = gmd)
electronic resource
InternetMediaType
application/pdf
InternetMediaType
text/xml
Extent
1 online resource (xxvi, 134 p. : ill.)
Note (type = degree)
Ph.D.
Note (type = bibliography)
Includes bibliographical references
Note (type = statement of responsibility)
by Lei Chen
RelatedItem (type = host)
TitleInfo
Title
Graduate School - Newark Electronic Theses and Dissertations
Identifier (type = local)
rucore10002600001
Location
PhysicalLocation (authority = marcorg); (displayLabel = Rutgers, The State University of New Jersey)
I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.