Site-Isolation, Intramolecular Energy Transfer, and Crosslinking in Synthetic Dendritic Quinacridones

Persistent Link:
http://hdl.handle.net/10150/195596
Title:
Site-Isolation, Intramolecular Energy Transfer, and Crosslinking in Synthetic Dendritic Quinacridones
Author:
D'Ambruoso, Gemma Delcina
Issue Date:
2005
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:
Dendrimers incorporating a green emitter, quinacridone, for organic light emitting diodes (OLEDs) were synthesized and their photophysical and electrochemical properties were explored. Quinacridone dendrimers were synthesized for site isolation, intramolecular energy transfer, and photocrosslinking.Site-isolation of quinacridone at the core of a dendrimer was achieved by attaching bulky poly(aryl ether) dendrons to the quinacridone at the amino functional groups. Both benzyl- and t-butyl-terminated dendrimers were synthesized up to the third generation. These dendrimers showed enhanced solubility in organic solvents due to reduced aggregation and hydrogen bonding. Increased photoluminescence intensity was observed for the denderimers in the solid state indicating reduced self-quenching due to enhanced site-isolation. Preliminary incorporation of these dendrimers as dopants into OLEDs showed increased emission from the dendrimers as the doping percentage increases.When high-energy host absorbing groups, such as oligo(p-phenylene vinylene)s (oPPVs) were placed at the periphery of poly (aryl ether) dendrimers with quinacridone guest cores, intramolecular energy transfer occurs when the host periphery groups were excited. These dendrimers showed high efficiency energy transfer yields in both solution and the solid state, as well as an antennae effect which resulted in increased emission when the oPPVs were excited versus direct excitation of the quinacridone. For comparison, poly (methyl methacrylate) polymers with pendant oPPV groups were synthesized and combined both in solution and in thin films with the site-isolated dendrimers to investigate the architectural requirements for energy transfer. These mixtures showed no energy transfer in solution from the polymer to the dendrimers. However, in the solid state, energy transfer increaseed with decreasing generation due to the host/guest chromophores decreased separation.Finally, poly (aryl ether) dendrimers containing photocrosslinkable cinnamate groups at the periphery and quinacridone cores were synthesized. Thin films of the higher generation dendrimers were photopolymerized via ultraviolet irradiation. The films were resistant to solvent after the polymerization step indicating a stable crosslinked network. Standard photolithography was performed on the higher generation dendrimers to achieve feature sizes as small as 5 microns as observed by fluorescence and atomic force microscopy.
Type:
text; Electronic Dissertation
Keywords:
Chemistry
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.titleSite-Isolation, Intramolecular Energy Transfer, and Crosslinking in Synthetic Dendritic Quinacridonesen_US
dc.creatorD'Ambruoso, Gemma Delcinaen_US
dc.contributor.authorD'Ambruoso, Gemma Delcinaen_US
dc.date.issued2005en_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.abstractDendrimers incorporating a green emitter, quinacridone, for organic light emitting diodes (OLEDs) were synthesized and their photophysical and electrochemical properties were explored. Quinacridone dendrimers were synthesized for site isolation, intramolecular energy transfer, and photocrosslinking.Site-isolation of quinacridone at the core of a dendrimer was achieved by attaching bulky poly(aryl ether) dendrons to the quinacridone at the amino functional groups. Both benzyl- and t-butyl-terminated dendrimers were synthesized up to the third generation. These dendrimers showed enhanced solubility in organic solvents due to reduced aggregation and hydrogen bonding. Increased photoluminescence intensity was observed for the denderimers in the solid state indicating reduced self-quenching due to enhanced site-isolation. Preliminary incorporation of these dendrimers as dopants into OLEDs showed increased emission from the dendrimers as the doping percentage increases.When high-energy host absorbing groups, such as oligo(p-phenylene vinylene)s (oPPVs) were placed at the periphery of poly (aryl ether) dendrimers with quinacridone guest cores, intramolecular energy transfer occurs when the host periphery groups were excited. These dendrimers showed high efficiency energy transfer yields in both solution and the solid state, as well as an antennae effect which resulted in increased emission when the oPPVs were excited versus direct excitation of the quinacridone. For comparison, poly (methyl methacrylate) polymers with pendant oPPV groups were synthesized and combined both in solution and in thin films with the site-isolated dendrimers to investigate the architectural requirements for energy transfer. These mixtures showed no energy transfer in solution from the polymer to the dendrimers. However, in the solid state, energy transfer increaseed with decreasing generation due to the host/guest chromophores decreased separation.Finally, poly (aryl ether) dendrimers containing photocrosslinkable cinnamate groups at the periphery and quinacridone cores were synthesized. Thin films of the higher generation dendrimers were photopolymerized via ultraviolet irradiation. The films were resistant to solvent after the polymerization step indicating a stable crosslinked network. Standard photolithography was performed on the higher generation dendrimers to achieve feature sizes as small as 5 microns as observed by fluorescence and atomic force microscopy.en_US
dc.typetexten_US
dc.typeElectronic Dissertationen_US
dc.subjectChemistryen_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.committeememberHall, Henry K., Jr.en_US
dc.contributor.committeememberGhosh, Indraneelen_US
dc.contributor.committeememberSaavedra, S. Scotten_US
dc.contributor.committeememberArmstrong, Neal R.en_US
dc.identifier.proquest1135en_US
dc.identifier.oclc137354143en_US
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