Synthesis and polymerization of supramolecular assemblies of octasubstituted phthalocyanines

Persistent Link:
http://hdl.handle.net/10150/279826
Title:
Synthesis and polymerization of supramolecular assemblies of octasubstituted phthalocyanines
Author:
Drager, Anthony Steven
Issue Date:
2001
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:
Substituted phthalocyanines (Pc's) are an important class of organic molecules, which have shown promise in the field of organo-electronics. The goal of the current research was to synthesize a new class of polymerizable Pc's. It was hoped that the new class of compounds would exhibit similar liquid crystalline and self organization properties that had been demonstrated by 2,3,9,10,16,17,23,24-octakis(2-benzyoxyethoxy) phthalocyanine. This Pc formed stable Langmuir monolayer and bilayers, which could be transferred to solid supports without losing the long-range order. The initial reactive Pc was 2,3,9,10,16,17,23,24-octakis(2-benzyoxyethoxy) phthalocyanine. The monomer was a beta-substituted styrene that was located within the alkoxy chains, to prevent inter-columnar cross-linking. The styrene functionalities were dimerized (35% reaction) by photolysis at 254 nm to form cyclo-butanes. The rod-like polymers were characterized using AFM and MALDI-TOF mass spectral analysis and the molecular rods obtained had a mean length of 72 nm. The styrylethoxy Pc was shown to be more crystalline then the previous benzyloxyethoxy Pc's, in order to correct this a new class of reactive Pc's were developed that contained a second oxygen atom. DSC data on the cinnamyloxyethoxy Pc shows that the lower temperature for the liquid crystalline mesophase was restored. Polymerization experiments performed on the cinnamyloxyethoxy Pc showed faster and 2x higher percent conversion. The research detailed in this dissertation describes a novel Diels-Alder synthetic approach to this important class of molecules and a new generic route to polymer rods of Pc.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Chemistry, Organic.; Chemistry, Polymer.; Engineering, Materials Science.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Graduate College; Chemistry
Degree Grantor:
University of Arizona
Advisor:
O'Brien, David F.

Full metadata record

DC FieldValue Language
dc.language.isoen_USen_US
dc.titleSynthesis and polymerization of supramolecular assemblies of octasubstituted phthalocyaninesen_US
dc.creatorDrager, Anthony Stevenen_US
dc.contributor.authorDrager, Anthony Stevenen_US
dc.date.issued2001en_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.abstractSubstituted phthalocyanines (Pc's) are an important class of organic molecules, which have shown promise in the field of organo-electronics. The goal of the current research was to synthesize a new class of polymerizable Pc's. It was hoped that the new class of compounds would exhibit similar liquid crystalline and self organization properties that had been demonstrated by 2,3,9,10,16,17,23,24-octakis(2-benzyoxyethoxy) phthalocyanine. This Pc formed stable Langmuir monolayer and bilayers, which could be transferred to solid supports without losing the long-range order. The initial reactive Pc was 2,3,9,10,16,17,23,24-octakis(2-benzyoxyethoxy) phthalocyanine. The monomer was a beta-substituted styrene that was located within the alkoxy chains, to prevent inter-columnar cross-linking. The styrene functionalities were dimerized (35% reaction) by photolysis at 254 nm to form cyclo-butanes. The rod-like polymers were characterized using AFM and MALDI-TOF mass spectral analysis and the molecular rods obtained had a mean length of 72 nm. The styrylethoxy Pc was shown to be more crystalline then the previous benzyloxyethoxy Pc's, in order to correct this a new class of reactive Pc's were developed that contained a second oxygen atom. DSC data on the cinnamyloxyethoxy Pc shows that the lower temperature for the liquid crystalline mesophase was restored. Polymerization experiments performed on the cinnamyloxyethoxy Pc showed faster and 2x higher percent conversion. The research detailed in this dissertation describes a novel Diels-Alder synthetic approach to this important class of molecules and a new generic route to polymer rods of Pc.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectChemistry, Organic.en_US
dc.subjectChemistry, Polymer.en_US
dc.subjectEngineering, Materials Science.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorO'Brien, David F.en_US
dc.identifier.proquest3026553en_US
dc.identifier.bibrecord.b42177376en_US
All Items in UA Campus Repository are protected by copyright, with all rights reserved, unless otherwise indicated.