Development of Phosphonate Monoester-Based Coordination Frameworks
| dc.contributor.advisor | Shimizu, George | |
| dc.contributor.author | Gelfand, Benjamin | |
| dc.contributor.committeemember | Roesler, Roland | |
| dc.contributor.committeemember | Marriott, Robert | |
| dc.contributor.committeemember | Mahinpey, Nader | |
| dc.contributor.committeemember | Li, Qiaowei | |
| dc.date | 2018-06-07 | |
| dc.date.accessioned | 2018-04-26T22:09:17Z | |
| dc.date.available | 2018-04-26T22:09:17Z | |
| dc.date.issued | 2018-04-26 | |
| dc.description.abstract | This thesis emphasizes the development and gas sorption properties of metal-phosphonate monoester compounds. The first chapter discusses hydrolytic stability in metal-organic frameworks, with a focus on the types of hydrolytic exposure and assessing stability. The next four chapters focus on the synthesis and characterization of seven new coordination compounds. The first three compounds (2-4) are compared and contrasted to a pillared-layered material consisting of barium and a linear diphosphonate (1); 2 is based on a planar triphosphonate analogue, 3 is based on a linear diphosphonate bis(monoester), and 4 is based on a planar triphosphonate tris(monoester). Though none of these materials have any function, comparisons of 1-4 has allowed several structural trends to be determined, notably that both the change from diphosphonate to triphosphonate and from phosphonate to phosphonate monoester result in the building units in 1 being truncated. 5 is based on the same linear ditopic phosphonate monoester as 3 but with copper(II) and is insoluble and stable in water, a feature not often seen with similar building units. 6 was synthesized based on the stability and building unit found in 5 but with the planar tritopic phosphonate monoester used in 4. 6 is a permanently porous material with a surface area exceeding 300 m^2/g. Though the same level of stability is not found in 6 as in 5, 6 was found to retain its crystallinity and porosity even in steam-like conditions. In an attempt to increase the porosity of 6, a longer linker was synthesized and used to make 7 and 8. 8 was found to be highly porous (>1000 m^2/g) and it was also discovered that one of the esters in 8 can be systematically hydrolyzed in situ in order to increase the materials affinity for CO2. Furthermore, experimental results and simulations for 8 conclude that the removal of these esters is randomly distributed in the framework, rather than being clustered. Though 7 is non-porous and no function has been found, it is made from nearly identical building units to 8, allowing for potential synthetic factors to be considered and discussed. | en_US |
| dc.identifier.citation | Gelfand, B. S. (2018). Development of Phosphonate Monoester-Based Coordination Frameworks (Doctoral thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca. doi:10.11575/PRISM/31847 | en_US |
| dc.identifier.doi | http://dx.doi.org/10.11575/PRISM/31847 | |
| dc.identifier.uri | http://hdl.handle.net/1880/106561 | |
| dc.language.iso | eng | |
| dc.publisher.faculty | Graduate Studies | |
| dc.publisher.faculty | Science | |
| dc.publisher.institution | University of Calgary | en |
| dc.publisher.place | Calgary | en |
| dc.rights | University of Calgary graduate students retain copyright ownership and moral rights for their thesis. You may use this material in any way that is permitted by the Copyright Act or through licensing that has been assigned to the document. For uses that are not allowable under copyright legislation or licensing, you are required to seek permission. | |
| dc.subject.classification | Materials Science | en_US |
| dc.title | Development of Phosphonate Monoester-Based Coordination Frameworks | |
| dc.type | doctoral thesis | |
| thesis.degree.discipline | Chemistry | |
| thesis.degree.grantor | University of Calgary | |
| thesis.degree.name | Doctor of Philosophy (PhD) | |
| ucalgary.item.requestcopy | true |