Metal organic frameworks (MOFs) are metal-ligand compounds that extend into one, two or three dimensions via metal-ligand bonding that have found numerous technological applications, associated with their open pores and large internal surface area. The work developed in this doctoral thesis consists in the study of methodologies and systematic development of ligands or organic spacers for the synthesis of novel metal organic frameworks.
An introduction to the chemistry, structural features and diverse applications of metal organic frameworks is provided in Chapter 1.
The following chapter, chapter 2 involves the synthesis of gallium, indium and thallium metal organic frameworks using pyrazine, and pyrazine-2-carboxylic acid as organic spacers. The change in the pore size of the synthesized frameworks was studied in correlation with the atomic radii of the selected triel elements.
Chapter 3 describes the work with the flexible, multidentate heteroelemental dipodal ligands: bis(2-pyridylthio)methane, bis(2-pyrimidylthio)methane and bipyrimidyldisulfide. These ligands were reacted with a series of copper halides or pseudo halides for the isolation of cubane clusters and polymers depending on the flexibility of the selected ligands, the stereochemical requirements of the metal center and the preferred coordination modes of the corresponding halide or pseudo halide.
The fourth chapter deals with the use of 2-pyridinephosphonic acid (2PyPOH2), 4-pyridinephosphonic acid (4PyPOH2) and 4-pyridinemethylphosphonic acid (4PyCH2PO3H2) for the synthesis of aluminum and gallium phosphonate cages. The isolation of these cages was achieved under careful control of the hydrolytic conditions of the corresponding reaction media.
Chapter 5, details the results of the studies with the ligand aminomethylphosphonic acid (ampa) for the construction of MOFs. The reaction of ampa with salts of Zn, Cd, Hg, Pb, Ag, Cu and Pb afforded new metal-phosphonate polymers with unique structural features and includes the synthesis of a bimetallic MOF containing Ag and Cu.
Finally, chapter 6 analyzes the ligand 5-pyrimidyl phosphonic acid (5-PymPO3H2) in the synthesis of homo and heteroelemental MOFs based on its possession of a phosphonate moiety for coordination and two heterocyclic nitrogen atoms at the opposite end to the PO3H2 to promote multi-site coordination. As a consequence it was possible to synthesize six coordination polymers, including a two dimensional, Cu/Ag polymer.
All of the MOFs obtained throughout these studies have been characterized by X-ray crystallography along with other spectroscopic techniques, including NMR, IR, UV/Vis, and MS.
| Identifer | oai:union.ndltd.org:TCU/oai:etd.tcu.edu:etd-04232009-112540 |
| Date | 23 April 2009 |
| Creators | Samanamu, Christian Roberto |
| Contributors | Anne F. Richards |
| Publisher | Texas Christian University |
| Source Sets | Texas Christian University |
| Language | English |
| Detected Language | English |
| Type | text |
| Format | application/pdf, application/msword |
| Source | http://etd.tcu.edu/etdfiles/available/etd-04232009-112540/ |
| Rights | unrestricted, I hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to TCU or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report. |
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