{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/145046"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/145046","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Controlling the Properties of Polymer Metal-Organic Frameworks and Cages Through Polymer Ligand Design","abstract":"Chapter 1: Synthetic and Design Considerations in Polymer Metal Organic Frameworks and Cages Strategies for developing polymer-tethered MOF/MOC hybrid materials are discussed. Emphasis is place on the impacts of synthetic strategy and polymer ligand design on the properties and applications of the end material. Chapter 2: PolyMOF Nanoparticles: Dual Roles of a Multivalent polyMOF Ligand in Size Control and Surface Functionalization A simple strategy to access functional MOF nanoparticles in one pot is reported using a ligand possessing a polymer block for surface functionalization and a coordination block with tunable multivalency for size control. This strategy produces uniform polyMOF-5 and polyUiO66 nanoparticles with sizes down to 20 nm, displaying exceptional structural and colloidal stability. Chapter 3: Radical PolyMOFs: A Role for Ligand Dispersity in Enabling Crystallinity Reported here is the synthesis of polyMOF ligands featuring MOF-forming linkers on their sidechains using common radical polymerization techniques: reversible addition fragmentation chain transfer (RAFT) polymerization and free radical polymerization (FRP). High-dispersity ligands prepared through FRP formed crystalline polyMOFs while low-dispersity RAFT ligands required the addition of free H2bdc to yield crystalline materials analogous to MOF-5 and UiO-66, suggesting that ligand dispersity is a key design parameter for polyMOF synthesis. Chapter 4: Mixed Ligands as a General Strategy for Tuning the Properties of polyMOFs and the Synthesis of MTV-polyMOFs A strategy of mixing free linker with a step-growth polymer ligand containing MOFforming linkers is investigated as a means to tune modify the properties of polyMOFs, resulting in polyMOFs with superior N2 and CO2 uptake. The strategy is further studied by combining distinct MOF-forming polymer ligands to create MTV-polyMOFs, presenting a method for incorporating low-dispersity polymer ligands with complex architectures into polyMOF lattices without the addition of small molecule components. Chapter 5: Polymer Metal Organic Cages from RAFT Polymerization Here, a RAFT polymer ligand for the synthesis of Cu-paddlewheel, isophthalic acidbased bulk polyMOC powders is developed. The crystallinity and morphology of the polyMOCs can be tuned by addition of varying amounts of free isophthalic acid. These polymer/MOC hybrids represent a unique morphology and provide a platform for the synthesis of more complex hybrids.","abstract_html":"Chapter 1: Synthetic and Design Considerations in Polymer Metal Organic Frameworks and Cages Strategies for developing polymer-tethered MOF/MOC hybrid materials are discussed. Emphasis is place on the impacts of synthetic strategy and polymer ligand design on the properties and applications of the end material. Chapter 2: PolyMOF Nanoparticles: Dual Roles of a Multivalent polyMOF Ligand in Size Control and Surface Functionalization A simple strategy to access functional MOF nanoparticles in one pot is reported using a ligand possessing a polymer block for surface functionalization and a coordination block with tunable multivalency for size control. This strategy produces uniform polyMOF-5 and polyUiO66 nanoparticles with sizes down to 20 nm, displaying exceptional structural and colloidal stability. Chapter 3: Radical PolyMOFs: A Role for Ligand Dispersity in Enabling Crystallinity Reported here is the synthesis of polyMOF ligands featuring MOF-forming linkers on their sidechains using common radical polymerization techniques: reversible addition fragmentation chain transfer (RAFT) polymerization and free radical polymerization (FRP). High-dispersity ligands prepared through FRP formed crystalline polyMOFs while low-dispersity RAFT ligands required the addition of free H2bdc to yield crystalline materials analogous to MOF-5 and UiO-66, suggesting that ligand dispersity is a key design parameter for polyMOF synthesis. Chapter 4: Mixed Ligands as a General Strategy for Tuning the Properties of polyMOFs and the Synthesis of MTV-polyMOFs A strategy of mixing free linker with a step-growth polymer ligand containing MOFforming linkers is investigated as a means to tune modify the properties of polyMOFs, resulting in polyMOFs with superior N2 and CO2 uptake. The strategy is further studied by combining distinct MOF-forming polymer ligands to create MTV-polyMOFs, presenting a method for incorporating low-dispersity polymer ligands with complex architectures into polyMOF lattices without the addition of small molecule components. Chapter 5: Polymer Metal Organic Cages from RAFT Polymerization Here, a RAFT polymer ligand for the synthesis of Cu-paddlewheel, isophthalic acidbased bulk polyMOC powders is developed. The crystallinity and morphology of the polyMOCs can be tuned by addition of varying amounts of free isophthalic acid. These polymer/MOC hybrids represent a unique morphology and provide a platform for the synthesis of more complex hybrids.","abstract_has_math":false,"creators":["Pearson, Matthew A."],"institution":"Massachusetts Institute of Technology","degree_name":"Doctoral","degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Department of Chemistry","school":null,"contributors":[],"advisors":["Johnson, Jeremiah A."],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-05","date_published":"2022-05","updated_at":"2026-07-22T22:20:48Z","subjects":[],"languages":[],"rights":["In Copyright - Educational Use Permitted","Copyright MIT"],"rights_urls":["http://rightsstatements.org/page/InC-EDU/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1721.1/145046","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Johnson, Jeremiah A."]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. 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Emphasis is place on the impacts of synthetic strategy and polymer ligand design on the properties and applications of the end material. Chapter 2: PolyMOF Nanoparticles: Dual Roles of a Multivalent polyMOF Ligand in Size Control and Surface Functionalization A simple strategy to access functional MOF nanoparticles in one pot is reported using a ligand possessing a polymer block for surface functionalization and a coordination block with tunable multivalency for size control. This strategy produces uniform polyMOF-5 and polyUiO66 nanoparticles with sizes down to 20 nm, displaying exceptional structural and colloidal stability. Chapter 3: Radical PolyMOFs: A Role for Ligand Dispersity in Enabling Crystallinity Reported here is the synthesis of polyMOF ligands featuring MOF-forming linkers on their sidechains using common radical polymerization techniques: reversible addition fragmentation chain transfer (RAFT) polymerization and free radical polymerization (FRP). High-dispersity ligands prepared through FRP formed crystalline polyMOFs while low-dispersity RAFT ligands required the addition of free H2bdc to yield crystalline materials analogous to MOF-5 and UiO-66, suggesting that ligand dispersity is a key design parameter for polyMOF synthesis. Chapter 4: Mixed Ligands as a General Strategy for Tuning the Properties of polyMOFs and the Synthesis of MTV-polyMOFs A strategy of mixing free linker with a step-growth polymer ligand containing MOFforming linkers is investigated as a means to tune modify the properties of polyMOFs, resulting in polyMOFs with superior N2 and CO2 uptake. The strategy is further studied by combining distinct MOF-forming polymer ligands to create MTV-polyMOFs, presenting a method for incorporating low-dispersity polymer ligands with complex architectures into polyMOF lattices without the addition of small molecule components. Chapter 5: Polymer Metal Organic Cages from RAFT Polymerization Here, a RAFT polymer ligand for the synthesis of Cu-paddlewheel, isophthalic acidbased bulk polyMOC powders is developed. The crystallinity and morphology of the polyMOCs can be tuned by addition of varying amounts of free isophthalic acid. These polymer/MOC hybrids represent a unique morphology and provide a platform for the synthesis of more complex hybrids."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph.D."]},{"key":"dc:title","label":"Title","values":["Controlling the Properties of Polymer Metal-Organic Frameworks and Cages Through Polymer Ligand Design"]}]}],"canonical_facts":{"dc:contributor.advisor":["Johnson, Jeremiah A."],"dc:contributor.department":["Massachusetts Institute of Technology. Department of Chemistry"],"dc:creator":["Pearson, Matthew A."],"dc:date.accessioned":["2022-08-29T16:29:21Z"],"dc:date.available":["2022-08-29T16:29:21Z"],"dc:date.issued":["2022-05"],"dc:description.abstract":["Chapter 1: Synthetic and Design Considerations in Polymer Metal Organic Frameworks and Cages Strategies for developing polymer-tethered MOF/MOC hybrid materials are discussed. Emphasis is place on the impacts of synthetic strategy and polymer ligand design on the properties and applications of the end material. Chapter 2: PolyMOF Nanoparticles: Dual Roles of a Multivalent polyMOF Ligand in Size Control and Surface Functionalization A simple strategy to access functional MOF nanoparticles in one pot is reported using a ligand possessing a polymer block for surface functionalization and a coordination block with tunable multivalency for size control. This strategy produces uniform polyMOF-5 and polyUiO66 nanoparticles with sizes down to 20 nm, displaying exceptional structural and colloidal stability. Chapter 3: Radical PolyMOFs: A Role for Ligand Dispersity in Enabling Crystallinity Reported here is the synthesis of polyMOF ligands featuring MOF-forming linkers on their sidechains using common radical polymerization techniques: reversible addition fragmentation chain transfer (RAFT) polymerization and free radical polymerization (FRP). High-dispersity ligands prepared through FRP formed crystalline polyMOFs while low-dispersity RAFT ligands required the addition of free H2bdc to yield crystalline materials analogous to MOF-5 and UiO-66, suggesting that ligand dispersity is a key design parameter for polyMOF synthesis. Chapter 4: Mixed Ligands as a General Strategy for Tuning the Properties of polyMOFs and the Synthesis of MTV-polyMOFs A strategy of mixing free linker with a step-growth polymer ligand containing MOFforming linkers is investigated as a means to tune modify the properties of polyMOFs, resulting in polyMOFs with superior N2 and CO2 uptake. The strategy is further studied by combining distinct MOF-forming polymer ligands to create MTV-polyMOFs, presenting a method for incorporating low-dispersity polymer ligands with complex architectures into polyMOF lattices without the addition of small molecule components. Chapter 5: Polymer Metal Organic Cages from RAFT Polymerization Here, a RAFT polymer ligand for the synthesis of Cu-paddlewheel, isophthalic acidbased bulk polyMOC powders is developed. The crystallinity and morphology of the polyMOCs can be tuned by addition of varying amounts of free isophthalic acid. These polymer/MOC hybrids represent a unique morphology and provide a platform for the synthesis of more complex hybrids."],"dc:description.degree":["Ph.D."],"dc:identifier.uri":["https://hdl.handle.net/1721.1/145046"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["In Copyright - Educational Use Permitted","Copyright MIT"],"dc:rights.uri":["http://rightsstatements.org/page/InC-EDU/1.0/"],"dc:title":["Controlling the Properties of Polymer Metal-Organic Frameworks and Cages Through Polymer Ligand Design"],"dc:type":["Thesis"],"thesis:degree_name":["Doctoral","Doctor of Philosophy"]},"updated_at":"2026-07-22T22:20:48Z"}