Charge transfer complexes of polymers containing pendant heterocyclic rings.
Item
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Title
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Charge transfer complexes of polymers containing pendant heterocyclic rings.
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Identifier
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AAI9009774
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identifier
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9009774
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Creator
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Rodriguez, Libaniel.
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Contributor
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Adviser: Nan-Loh Yang
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Date
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1989
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, General | Chemistry, Polymer | Chemistry, Organic
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Abstract
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Charge-transfer complexes of a series of three polymers containing pendant heterocyclic polar rings, poly(2-vinylpyridine), P2VP, poly(3-vinylpyridazine), P3VPd, and poly(4-vinylpyridazine), P4VPd, with iodine were studied. The P2VP polymer, upon complex formation with iodine at low temperatures, led to crosslinking and degradation of the polymer as well as generation of paramagnetic centers in the complex. These phenomena were not observed for the polymers P3VPd and P4VPd under the same conditions. The difference in behaviour was ascribed to the higher resonance energy of pyridine compared to pyridazine.;For the study of the P3VPd-I{dollar}\sb2{dollar} and P4VPd-I{dollar}\sb2{dollar} systems, two new polymers, P3VPd and P4VPd, and their monomers, 3- and 4-vinylpyridazine, as well as their precursor alcohols, 3- and 4- ({dollar}\beta{dollar}-hydroxyethyl)pyridazine were synthesized and characterized for the first time by us. Our study of the new polymers showed that the differences in direction and magnitude of the dipole moment of the pendant pyridazine rings were responsible for the stereoregularity of the polymers. Dipole interactions were found to cause significant differences in dilute solution viscosity as well as thermal behaviour of the two polymers. For radical P4VPd, an unusual rigid rod structure leading to liquid crystalline behaviour, not found in P3VPd, was observed. The synthesis of the two new intermediate alcohols, 3- and 4-{dollar}\beta{dollar}-(hydroxyethyl)pyridazine required the development of a new anhydrous molecular formaldehyde reagent solution which we employed successfully. We showed these anhydrous solutions with controlled concentrations of molecular formaldehyde to be effective in the addition of one carbon to organometallic species including Grignard reagents and demonstrated their broad potential for organic synthesis.;Charge-transfer complex formation of the new polymers with iodine resulted in adducts with direct current conductivity at least in the same range as the semi-conductive P2VP- iodine system, i.e. 10{dollar}\sp{lcub}-5{rcub}{dollar} to 10{dollar}\sp{lcub}-4{rcub}{dollar} {dollar}\Omega{dollar} {dollar}\cdot{dollar} cm{dollar}\sp{lcub}-1{rcub}{dollar}.;The two new polymers showed better thermal stability compared to P2VP. This property, combined with semiconductive behaviour and special properties such as rigid rod and liquid crystal behaviour, suggests clearly that polymers with heterocyclic pendant rings can be competitive systems to the unstable, highly conjugated backbone, charge-transfer complexes studied extensively in the past two decades.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
