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dc.contributor.advisorNeilson, Robert H.
dc.contributor.authorFry, Julie Annen_US
dc.date.accessioned2014-07-22T18:48:15Z
dc.date.available2014-07-22T18:48:15Z
dc.date.created2011en_US
dc.date.issued2011en_US
dc.identifieretd-12132011-150817en_US
dc.identifierumi-10272en_US
dc.identifiercat-001784018en_US
dc.identifier.urihttps://repository.tcu.edu:443/handle/116099117/4311
dc.description.abstractMetal-organic frameworks (MOFs) are dynamic three-dimensional networks that reveal unprecedented gas adsorption and storage capabilities, catalytic function, and other useful properties such as luminescence and magnetism. While we begin to see many possibilities for applications of these polymers, the goal of true rational design will only be achieved on the basis of intensive systematic investigations. The following five chapters will detail our efforts to advance the research goal of utilizing mild synthetic methods to investigate factors controlling the structure of crystalline, thermally stable coordination polymers utilizing N-functionalized phosphonic acids. Studies into preferred metal geometry and coordination modes, ligand flexibility, counterion, solvent, and pH will be addressed to discern useful patterns for future synthetic endeavors. Chapter 1 presents an introduction to the terminology, structural diversity, and chemical applications of this emerging field.^Chapter 2 describes the synthesis and crystallographic analysis of five polymers employing a bifunctional, zwitterionic 2-(pyridyl)phosphonic acid ligand, 2PyHPO3H, and salts of Zn(II), Cd(II), Hg(II), and Ag(I). Chapter 3 reports the influence that cation choice and ligand flexibility have on the dimensionality and structure of eight products containing Mn(II), Co(II), Fe(II), Fe(III), Ag(I), and Pb(II) cations and 2-(pyridylmethyl)phosphonic acid, 2PyCH2PO3H2. Chapter 4 explores the use of (aminomethyl)phosphonic acid (NH3CH2PO3H) as a bifunctional organic linker for the production of coordination polymers. The substitution of the amino group for the rigid heterocyclic ring of 2-(pyridylmethyl)phosphonic acid results in two-dimensional organophosphonate frameworks with Zn(II), Mn(II), Co(II), Cu(II), Gd(III), Sm(III), and Yb(III) cations.^Chapter 5 relates our efforts to evaluate the relationships between metal choice, counterion, and ligand geometric constraints on polymer architectures. Ca(II), Co(II) and Zn(II) salts produce both dimers and polymers with 2-(pyridylmethyl)phosphonic acid, and Ag(I) and Zn(II) salts form unique polymers with 3- and 4-(pyridylmethyl)phosphonic acid. Crystal structures of the compounds allow us to compare and contrast the final products of the self-assembly process. Other analytical techniques, such as IR, NMR, TGA, and mass spectroscopy, are used to support and interpret the crystallographic results.en_US
dc.format.mediumFormat: Onlineen_US
dc.language.isoengen_US
dc.publisher[Fort Worth, Tex.] : Texas Christian University,en_US
dc.relation.ispartofTexas Christian University dissertationen_US
dc.relation.ispartofUMI thesis.en_US
dc.relation.ispartofTexas Christian University dissertation.en_US
dc.relation.requiresMode of access: World Wide Web.en_US
dc.relation.requiresSystem requirements: Adobe Acrobat reader.en_US
dc.subject.lcshCrystalline polymers.en_US
dc.subject.lcshPhosphonic acids.en_US
dc.subject.lcshCoordination polymers.en_US
dc.subject.lcshX-ray crystallography.en_US
dc.titleCrystallographic studies for the rational design of N-functionalized phosphonic acid coordination polymersen_US
dc.typeTexten_US
etd.degree.departmentDepartment of Chemistry
etd.degree.levelDoctoral
local.collegeCollege of Science and Engineering
local.departmentChemistry and Biochemistry
local.academicunitDepartment of Chemistry and Biochemistry
dc.type.genreDissertation
local.subjectareaChemistry and Biochemistry
etd.degree.nameDoctor of Philosophy
etd.degree.grantorTexas Christian University


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