LIU, CHONG
(2016)
POSTSYNTHETIC CONTROL OF FUNCTIONALITY AND POROSITY IN METAL-ORGANIC FRAMEWORKS USING COVALENT, COORDINATIVE, AND ELECTROSTATIC INTERACTIONS.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
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Abstract
Metal-organic frameworks (MOFs) are a versatile family of hybrid materials. Research attention and industrial interest have focused on MOFs because of their diverse properties and their tunable host-guest interactions/chemistry. MOFs are intrinsically porous, and the porosity underlies many of their properties and applications. Methods for systematically controlling MOF porosity and functionality provide a gateway to new frontiers of MOF research. In this dissertation, I present four research projects aimed at fine-tuning MOF porosity and functionality in order to create materials with functionally- and structurally-complex pore environments.
Specifically, in Chapter 2, a versatile and nearly quantitative method is presented to covalently modify MOFs, especially mesoporous MOFs, with organic and biological molecules via strain-promoted click chemistry. In Chapter 3, a sequential postsynthetic ligand exchange protocol is presented for introducing up to three orthogonal functional groups into the MOF pore space. Subsequently, a new fluorescence-based method is implemented to experimentally reveal the macroscopic distribution of functional groups within individual MOF crystals by introducing fluorophore and quencher molecules. In Chapter 4, construction of porosity gradients within individual mesoporous MOF crystals via ligand exchange-based partial pore expansion is described. The product MOF crystals, bearing a hierarchical distribution of domains having differential porosity, are used to organize nano-sized molecules in a heterogeneous fashion. In Chapter 5, a series of isoreticular rare earth MOFs having the well-known fcu topology is introduced. Based on their anionic nature, cation exchange experiments are applied to incorporate chromophore guest molecules. One of the incorporated dye compounds is used as an antenna molecule to sensitize Yb3+ in the MOF.
The research described represents a significant step forward in the development of MOF chemistry and will enable new studies that focus on using MOFs as platform materials for precisely organizing complex molecules and nanoscale materials in three-dimensional space.
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Details
| Item Type: |
University of Pittsburgh ETD
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| Status: |
Unpublished |
| Creators/Authors: |
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| ETD Committee: |
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| Date: |
30 September 2016 |
| Date Type: |
Publication |
| Defense Date: |
23 June 2016 |
| Approval Date: |
30 September 2016 |
| Submission Date: |
22 July 2016 |
| Access Restriction: |
2 year -- Restrict access to University of Pittsburgh for a period of 2 years. |
| Number of Pages: |
318 |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
| Degree: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
metal-organic frameworks, postsynthetic modification, ligand exchange, porosity gradient, cation exchange, lanthanide photoluminescence, |
| Related URLs: |
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| Date Deposited: |
30 Sep 2016 19:43 |
| Last Modified: |
30 Sep 2018 05:15 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/28994 |
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