Copenhafer, James Edward
(2007)
Synthesis and Characterization of Poly(9,9-Dihexylfluorene-mb-methylene)s.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
The synthesis and characterization of copolymers possessing exact repeating sequences of 9,9-dihexylfluorene and methylene repeat units are described. Each poly(9,9-dihexylfluorene-mb-methylene) (PFM, mb = multiblock) was synthesized following the assembly of a symmetrically disubstituted monodisperse oligofluorene. Alkyl segments possessing terminal alkene functionality were then coupled at both of the substituted positions on the oligofluorene to give a macromolecular "segmer" compound. Each segmer was polymerized using Acyclic Diene Metathesis (ADMET) and, following post-polymerization hydrogenation, a PFM with an entirely repeating diblock sequence was produced. PFMs possessing 9,9-dihexylfluorene segment lengths of x = 1, 2, 3, 4, 7, or 8 units and methylene segment lengths of y = 10 or 18 units were prepared to give a ten member PFM library. As PFMs have exact chemical compositions and monomer unit sequencing, studies aimed at elucidating solution and bulk phase trends were performed. Spectroscopic characteristics that make polyfluorene-type materials attractive include their generally efficient blue light emission (λmax ~ 448 nm). Successful investigations into the optical tuning of PFMs in solution and in the bulk are described. Additionally, thermal- and photostabilities of PFMs under a variety of conditions are reported and compared to the related homopolymer, poly(9,9-dihexylfluorene) [PDHF]. Compared to PDHF, PFMs display similar, and in some cases superior resistance to photobleaching processes. Additionally, thermal and photostability investigations into keto-induced degradation processes of PFMs suggest that interruption of the fluorene segments with alkyl spacers effectively suppresses intrachain charge migration and interchain Förster energy transfer in the bulk. The rate of PFM, and likewise PDHF degradation was found to be at least partially dependent on the initial state of the sample.Efforts toward the transition metal-catalyzed production of cyclic oligomers are described. Two rigid bifunctional molecules bearing both transition-metal metathesis initiating and terminating groups were prepared. The synthesis and metathesis activity of these compounds are reported.
Share
| Citation/Export: |
|
| Social Networking: |
|
Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
|
| Date: |
29 January 2007 |
| Date Type: |
Completion |
| Defense Date: |
6 November 2006 |
| Approval Date: |
29 January 2007 |
| Submission Date: |
29 October 2006 |
| Access Restriction: |
5 year -- Restrict access to University of Pittsburgh for a period of 5 years. |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
| Degree: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
OLED; polymer |
| Other ID: |
http://etd.library.pitt.edu/ETD/available/etd-10292006-104853/, etd-10292006-104853 |
| Date Deposited: |
10 Nov 2011 20:03 |
| Last Modified: |
15 Nov 2016 13:51 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/9538 |
Metrics
Monthly Views for the past 3 years
Plum Analytics
Actions (login required)
 |
View Item |
![[feed]](/images/feed-icon-32x32.png){kind=icon}