I. Tunable Luminescence in Dendronized Poly(phenyleneethynylene)s Through Post-Polymerization Chemical Modification II. Rigid, Helical Polymers Based Upon Chiral Hydrobenzoin

Persistent Link:
http://hdl.handle.net/10150/194768
Title:
I. Tunable Luminescence in Dendronized Poly(phenyleneethynylene)s Through Post-Polymerization Chemical Modification II. Rigid, Helical Polymers Based Upon Chiral Hydrobenzoin
Author:
Sisk, David Theodore
Issue Date:
2007
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
Dendritic encapsulation of poly(phenyleneethynylene)s or PPEs has been shown to enhance photoluminescent quantum efficiency and facilitate energy transfer by funneling photonic energy absorbed on the dendron periphery efficiently to the conjugated polymeric core. The research presented herein focuses on incorporating degradable dendron onto PPEs, examining whether or not similar benefits were conferred upon the proposed system and controlling polymer luminescence through the elimination of the insulating macromolecules. PPEs appended with disassembling dendrons of various generation sizes were synthesized and their optical properties studied. Polymer luminescence was then quenched via chemical degradation of the disassembling dendrons. Furthermore, the macromolecules resulting from disassembly exhibited tunable luminescence properties upon manipulation of pH. Consequently, it was determined that polymer luminescence could be controlled upon forming phenolic moieties along the PPE backbone. Tunable emission was later realized in the thin film as well through the integration of crosslinkable dendrons onto the polymer core.Recently, helical synthetic linear polymers have demonstrated the ability to facilitate stereoselective processes such as catalysis, recognition and separation. Consequently, it has become increasingly desirable to develop new platforms capable of imparting asymmetry. The work presented herein describes the synthesis of a series of polymers based upon chiral hydrobenzoin and the subsequent conformational analysis performed on these materials. It was envisioned that these polymeric materials might inherently possess conformational asymmetry and as result could be able to impart configurationally chirality by introducing a diastereomeric bias for the formation of one enantiomer over the other during the course of the reaction.
Type:
text; Electronic Dissertation
Keywords:
dendronized PPEs; tunable luminescence; semiconducting polymers; hydrobenzoin-based polymers; helical polymers; conformational asymmetry
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
McGrath, Dominic V.
Committee Chair:
McGrath, Dominic V.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleI. Tunable Luminescence in Dendronized Poly(phenyleneethynylene)s Through Post-Polymerization Chemical Modification II. Rigid, Helical Polymers Based Upon Chiral Hydrobenzoinen_US
dc.creatorSisk, David Theodoreen_US
dc.contributor.authorSisk, David Theodoreen_US
dc.date.issued2007en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractDendritic encapsulation of poly(phenyleneethynylene)s or PPEs has been shown to enhance photoluminescent quantum efficiency and facilitate energy transfer by funneling photonic energy absorbed on the dendron periphery efficiently to the conjugated polymeric core. The research presented herein focuses on incorporating degradable dendron onto PPEs, examining whether or not similar benefits were conferred upon the proposed system and controlling polymer luminescence through the elimination of the insulating macromolecules. PPEs appended with disassembling dendrons of various generation sizes were synthesized and their optical properties studied. Polymer luminescence was then quenched via chemical degradation of the disassembling dendrons. Furthermore, the macromolecules resulting from disassembly exhibited tunable luminescence properties upon manipulation of pH. Consequently, it was determined that polymer luminescence could be controlled upon forming phenolic moieties along the PPE backbone. Tunable emission was later realized in the thin film as well through the integration of crosslinkable dendrons onto the polymer core.Recently, helical synthetic linear polymers have demonstrated the ability to facilitate stereoselective processes such as catalysis, recognition and separation. Consequently, it has become increasingly desirable to develop new platforms capable of imparting asymmetry. The work presented herein describes the synthesis of a series of polymers based upon chiral hydrobenzoin and the subsequent conformational analysis performed on these materials. It was envisioned that these polymeric materials might inherently possess conformational asymmetry and as result could be able to impart configurationally chirality by introducing a diastereomeric bias for the formation of one enantiomer over the other during the course of the reaction.en_US
dc.typetexten_US
dc.typeElectronic Dissertationen_US
dc.subjectdendronized PPEsen_US
dc.subjecttunable luminescenceen_US
dc.subjectsemiconducting polymersen_US
dc.subjecthydrobenzoin-based polymersen_US
dc.subjecthelical polymersen_US
dc.subjectconformational asymmetryen_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorMcGrath, Dominic V.en_US
dc.contributor.chairMcGrath, Dominic V.en_US
dc.contributor.committeememberMash, Eugene A.en_US
dc.contributor.committeememberPyun, Jeffreyen_US
dc.contributor.committeememberArmstrong, Neal R.en_US
dc.contributor.committeememberHall, H. K., Jr.en_US
dc.identifier.proquest2315en_US
dc.identifier.oclc659748173en_US
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