Assemblies of Metal-Organic Polyhedra: Synthesis, Properties and Characterization

dc.contributor.advisorShimizu, George K. H.
dc.contributor.authorLal, Garima
dc.contributor.committeememberTrudel, Simon
dc.contributor.committeememberLing, Changchun
dc.contributor.committeememberSundararaj, Uttandaraman
dc.contributor.committeememberUemura, Takashi
dc.date2019-11
dc.date.accessioned2019-09-06T18:21:28Z
dc.date.available2019-09-06T18:21:28Z
dc.date.issued2019-09-03
dc.description.abstractMetal-Organic Polyhedra (MOP) are nanoscale capsule-like supramolecular architectures composed of metal ions and organic linkers. They have well defined cavities depending on the ligand shape and metal-vertex geometry. The thesis concerns MOP composed of 12 copper(II) dimers (Cu24) and 24 isophthalate based linkers forming ~2 nm cuboctahedral structure. The isophthalates can be easily functionalized at 5th position with different chemical groups thereby giving surface functionalization to the Cu24MOPs. They are soluble depending upon the functional groups while retaining the structural integrity in solution. This offers rich solution chemistry and variety of potential applications. In this thesis, the versatility of Cu24MOPs has been utilized to create functional materials. Firstly, the degradation of a Cu24MOP is studied when exposed to water leading to formation of three coordination products at different time intervals (2,3 and 4). This study is crucial given the increasing use of MOPs for different purposes, to understand their outcomes when exposed to ubiquitous humidity/water. Secondly, long alkyl chain functionalized Cu24MOP, half of them having terminal alkenes have been synthesized (5) and utilized to create metal-organic framework (MOF) of different mechanical strength. This was done by cross-linking the MOP units via olefin metathesis and investigating mechanical properties through rheology and nanoindentation. Thirdly, Cu24MOPs functionalized with both polar and non-polar isophthalates were synthesized and the arrangement of linkers on the MOP surface i.e. symmetrical (6) and Janus-type (7 or ampMOP) were analyzed via crystallography and microscopy. Amphiphile-like self-assembly behavior of the Janus MOP was studied thoroughly. Lastly, mixed matrix membranes (MMM) using ampMOP and PEBAX polymer were created for usage in CO2/N2 gas separations. Overall, the thesis provides a reference for exploiting novel properties of MOPs.en_US
dc.identifier.citationLal, G. (2019). Assemblies of Metal-Organic Polyhedra: Synthesis, Properties and Characterization (Doctoral thesis, University of Calgary, Calgary, Canada). Retrieved from https://prism.ucalgary.ca.en_US
dc.identifier.doihttp://dx.doi.org/10.11575/PRISM/36947
dc.identifier.urihttp://hdl.handle.net/1880/110869
dc.publisher.facultyScienceen_US
dc.publisher.institutionUniversity of Calgaryen
dc.rightsUniversity 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.en_US
dc.subject.classificationEducation--Sciencesen_US
dc.titleAssemblies of Metal-Organic Polyhedra: Synthesis, Properties and Characterizationen_US
dc.typedoctoral thesisen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorUniversity of Calgaryen_US
thesis.degree.nameDoctor of Philosophy (PhD)en_US
ucalgary.item.requestcopytrueen_US
Files
Original bundle
Now showing 1 - 1 of 1
Loading...
Thumbnail Image
Name:
ucalgary_2019_lal_garima.pdf
Size:
15.03 MB
Format:
Adobe Portable Document Format
Description:
License bundle
Now showing 1 - 1 of 1
Loading...
Thumbnail Image
Name:
license.txt
Size:
2.62 KB
Format:
Item-specific license agreed upon to submission
Description: